Capsules

ABSTRACT

A population of capsules, the capsules can include a core including a benefit agent and a shell surrounding the core, wherein the shell can include a first shell component.

FIELD OF THE DISCLOSURE

The disclosure relates to capsules and methods of making capsules forthe transfer and triggered release of benefit agents.

BACKGROUND

Microencapsulation is a process where droplets of liquids, particles ofsolids or gasses are enclosed inside a solid shell and are generally inthe micro-size range. The core material is then mechanically separatedfrom the surrounding environment (Jyothi et al., Journal ofMicroencapsulation, 2010, 27, 187-197). Microencapsulation technology isattracting attention from various fields of science and has a wide rangeof commercial applications for different industries. Overall, capsulesare capable of one or more of (i) providing stability of a formulationor material via the mechanical separation of incompatible components,(ii) protecting the core material from the surrounding environment,(iii) masking or hiding an undesirable attribute of an active ingredientand (iv) controlling or triggering the release of the active ingredientto a specific time or location. All of these attributes can lead to anincrease of the shelf-life of several products and a stabilization ofthe active ingredient in liquid formulations.

Encapsulation can be found in areas such as pharmaceuticals, personalcare, textiles, food, coatings and agriculture. In addition, the mainchallenge faced by microencapsulation technologies in real-worldcommercial applications is that a complete retention of the encapsulatedactive within the capsule is required throughout the whole supply chain,until a controlled or triggered release of the core material is applied(Thompson et al., Journal of Colloid and Interface Science, 2015, 447,217-228). There are significantly limited microencapsulationtechnologies that are safe for both the environment and human healthwith a long-term retention and active protection capability that canfulfill the needs of the industry nowadays, especially when it comes toencapsulation of small molecules.

Over the past several years, consumer goods manufacturers have usedcore-shell encapsulation techniques to preserve actives, such as benefitagents, in harsh environments and to release them at the desired time,which may be during or after use of the consumer goods. Among theseveral mechanisms that can be used for release of benefit agent, theone commonly relied upon is mechanical rupture of the capsule shell.Selection of mechanical rupture as the release mechanism constitutesanother challenge to the manufacturer, as rupture must occur at specificdesired times, even if the capsules are subject to mechanical stressprior to the desired release time.

Industrial interest for encapsulation technology has led to thedevelopment of several polymeric capsules chemistries which attempt tomeet the requirements of low shell permeability, high deposition,targeted mechanical properties and rupture profile. Increasedenvironmental concerns have put the polymeric capsules under scrutiny,therefore manufacturers have started investigating sustainable solutionsfor the encapsulation of benefit agents. There is ample literature onsustainable capsules based on metal oxide or semi-metal oxides, mainlysilica capsules; however, none of the capsules described in theliterature provides the right balance of low shell permeability,mechanical properties, deposition, and rupture profile.

Capsules made with silane monomers only are known in the art. Multiplepatent applications and academic publications disclose the use ofmonomers such as tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS).The advantage of using such monomers is that they react faster thanprepolymers made from similar monomers, and as such have been thefavored option for years. This fast reaction time is due to their higherwater solubility once partially hydrolyzed compared to largerprecursors, due to the fact that the former have lower molecularweights, which accelerate further the overall hydrolysis kinetics asthey are in an excess of water once dispersed in said phase. However,these types of disclosures often use cationic surfactants such ascetyltrimethylammonium chloride (CTAC) or cetyltrimethylammonium bromide(CTAB), supposedly to drive the negatively charged hydrolyzedintermediate reaction species that are dispersed in the water phasetowards the oil/water interface.

Without wishing to be bound by theory, what is often the case is thatthe partially hydrolyzed monomers that are in an excess of water startcondensing and forming ever larger particulate sols that are drawn tooil/water interfaces. Ultimately, the system desires to reduce surfaceenergies of dispersed particulate sols by virtue of thermodynamic laws,which favors having the sols at the oil/water interfaces, especiallywhen they grow large. The formation of such particulate sols caneventually lead to a shell around oil droplets and in some cases evenshells that are strong enough towards mechanical self-integrity.However, by virtue of the geometrical properties (size, fractaldimensions, shapes etc.) of particulate sols, they are not able to formshells with a dense non-porous network that would provide low shellpermeability.

In addition, WO 2011/131644 discloses capsules with a semi-metal organicshell by joining together nanoparticles with the use of an oil solublesemi-metal precursor. However, the reference does not disclose a secondshell component. In the present invention it has been found that aselective choice of nanoparticles and precursors coupled with a secondshell component provides capsules that have reduced permeability andincreased mechanical integrity.

Without wishing to be bound by theory, the applicant has surprisinglyfound that a careful selection of primary shell components, secondaryshell components, nanoparticles, core-shell ratio, and thickness of theshell allows production of metal oxide or semi-metal oxide basedcapsules which hold their mechanical integrity once left air-drying on asurface and have low shell permeability in surfactant-based matrices.These two properties are the desired results but are alsocharacteristics of a dense and strong shell with low permeability madepossible only by the judicious choice of component materials andconditions to assemble them.

SUMMARY

A population of capsules is provided, the capsules comprising anoil-based core comprising a benefit agent, and a substantially inorganicshell surrounding the core, wherein the shell comprises a first shellcomponent comprising at least one of a metal oxide or a semi-metaloxide, wherein the first shell component comprises up to 5 wt % oforganic content; wherein said population has a mean volume weightedcapsule diameter of about 10 micrometers to about 200 micrometers, anaverage shell thickness of about 170 nm to about 1000 nm; and whereinthe mean volumetric core-shell ratio is from about 80:20 to about 98:2.

A population of capsules is provided, the capsules comprising awater-based core comprising a benefit agent, and a substantiallyinorganic shell surrounding the core, wherein the shell comprises afirst shell component comprising at least one of a metal oxide or asemi-metal oxide, wherein the first shell component comprises up toabout 5 wt % of organic content; wherein said population has a meanvolume weighted capsule diameter of about 10 micrometers to about 200micrometers, an average shell thickness of about 170 nm to about 1000nm; and wherein the mean volumetric core-shell ratio is from about 80:20to about 98:2.

A population of capsules is provided, the capsules comprising anoil-based core comprising a benefit agent, and a substantially inorganicshell surrounding the core, wherein the shell comprises a first shellcomponent comprising at least one of a metal oxide or a semi-metaloxide, wherein the first shell component comprises up to 5 wt % oforganic content; wherein said population has a mean volume weightedcapsule diameter of about 10 micrometers to about 200 micrometers, anaverage shell thickness of about 170 nm to about 1000 nm; and whereinthe mean volumetric core-shell ratio is from about 80:20 to about 98:2;wherein the first shell component comprises a condensed layer comprisinga condensation product of a precursor of at least one of formula (I) orformula (II) or both:

(M^(v)O_(z)Y_(n))_(w)  (Formula I),

where M is one or more of silicon, titanium and aluminum, v is thevalence number of M and is 3 or 4, z is from 0.5 to 1.6, each Y isindependently selected from —OH, —OR², halo,

—NH₂, —NHR², —N(R²)₂, and

wherein R² is a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ to C₂₂ aryl, ora 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatomsselected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ to C₂₀alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprising from1 to 3 ring heteroatoms selected from O, N, and S, n is from 0.7 to(v-1), and w is from 2 to 2000;

(M^(v)O_(z)Y_(n)R¹ _(p))_(w)  (Formula II),

where M is one or more of silicon, titanium and aluminum, v is thevalence number of M and is 3 or 4, z is from 0.5 to 1.6, each Y isindependently selected from —OH, —OR², halo,

NH₂, —NHR², —N(R²)₂,

wherein R² is selected from a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ toC₂₂ aryl, or a 5-12 membered heteroaryl comprising from 1 to 3 ringheteroatoms selected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ toC₂₀ alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprisingfrom 1 to 3 ring heteroatoms selected from O, N, and S, n is from 0 to(v-1), each R¹ is independently selected from a C₁ to C₃₀ alkyl, a C₁ toC₃₀ alkylene, a C₁ to C₃₀ alkyl substituted with one or more of ahalogen, —OCF₃, —NO₂, —CN, —NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino,mercapto, acryloyl, CO₂H, CO₂alkyl, aryl, and heteroaryl, or a C₁ to C₃₀alkylene substituted with one or more of a halogen, —OCF₃, —NO₂, —CN,—NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO₂H,CO₂alkyl, aryl, and heteroaryl, p is present in an amount up to pmax,and w is from 2 to 2000; wherein pmax=60/[9*Mw(R¹)+8], where Mw(R¹) isthe molecular weight of the R group.

A population of capsules is provided, the capsules comprising awater-based core comprising a benefit agent, and a substantiallyinorganic shell surrounding the core, wherein the shell comprises afirst shell component comprising at least one of a metal oxide or asemi-metal oxide, wherein the first shell component comprises up toabout 5 wt % of organic content; wherein said population has a meanvolume weighted capsule diameter of about 10 micrometers to about 200micrometers, an average shell thickness of about 170 nm to about 1000nm; and wherein the mean volumetric core-shell ratio is from about 80:20to about 98:2; wherein the first shell component comprises a condensedlayer comprising a condensation product of a precursor of at least oneof formula (I) or formula (II) or both:

(M^(v)O_(z)Y_(n))_(w)  (Formula I),

where M is one or more of silicon, titanium and aluminum, v is thevalence number of M and is 3 or 4, z is from 0.5 to 1.6, each Y isindependently selected from —OH, —OR², halo,

—NH₂, —NHR², —N(R²)₂, and

wherein R² is a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ to C₂₂ aryl, ora 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatomsselected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ to C₂₀alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprising from1 to 3 ring heteroatoms selected from O, N, and S, n is from 0.7 to(v-1), and w is from 2 to 2000;

(M^(v)O_(z)Y_(n)R¹ _(p))_(w)  (Formula II),

where M is one or more of silicon, titanium and aluminum, v is thevalence number of M and is 3 or 4, z is from 0.5 to 1.6, each Y isindependently selected from —OH, —OR², halo,

NH₂, —NHR², —N(R²)₂,

wherein R² is selected from a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ toC₂₂ aryl, or a 5-12 membered heteroaryl comprising from 1 to 3 ringheteroatoms selected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ toC₂₀ alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprisingfrom 1 to 3 ring heteroatoms selected from O, N, and S, n is from 0 to(v-1), each R¹ is independently selected from a C₁ to C₃₀ alkyl, a C₁ toC₃₀ alkylene, a C₁ to C₃₀ alkyl substituted with one or more of ahalogen, —OCF₃, —NO₂, —CN, —NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino,mercapto, acryloyl, CO₂H, CO₂alkyl, aryl, and heteroaryl, or a C₁ to C₃₀alkylene substituted with one or more of a halogen, —OCF₃, —NO₂, —CN,—NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO₂H,CO₂alkyl, aryl, and heteroaryl, p is present in an amount up to pmax,and w is from 2 to 2000; wherein pmax=60/[9*Mw(R¹)+8], where Mw(R¹) isthe molecular weight of the R group.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming the subject matter that is regarded as thepresent disclosure, it is believed that the disclosure will be morefully understood from the following description taken in conjunctionwith the accompanying drawings. Some of the figures may have beensimplified by the omission of selected elements for the purpose of moreclearly showing other elements. Such omissions of elements in somefigures are not necessarily indicative of the presence or absence ofparticular elements in any of the exemplary embodiments, except as maybe explicitly delineated in the corresponding written description. Noneof the drawings are necessarily to scale.

FIG. 1A is a schematic illustration of the method of making capsules inaccordance with an embodiment of the disclosure prepared with ahydrophobic core;

FIG. 2A is a scanning electron microscopy image of a capsule of sample Qin accordance with embodiments of the disclosure;

FIG. 2B is a scanning electron microscopy image of a capsule shell ofSample Q in accordance with embodiments of the disclosure;

FIG. 3A is a scanning electron microscopy image of a capsule of Sample Iin accordance with embodiments of the disclosure, illustrating anunbroken the capsule shell;

FIG. 3B is a scanning electron microscopy image of a cross-section of acapsule of Sample I in accordance with embodiments of the disclosure,illustrating a capsule shell;

FIG. 4A is a scanning electron microscopy image of capsules of Sample Ein accordance with embodiments of the disclosure;

FIG. 4B is a scanning electron microscopy image of a capsule shell ofSample E in accordance with embodiments of the disclosure;

FIG. 5 is an optical microscopy image of capsules of Sample C inaccordance with embodiments of the disclosure;

FIG. 6 is a scanning electron microscopy image of a capsule shell ofSample Z in accordance with embodiments of the disclosure;

FIG. 7A is a schematic illustration of a process of forming the secondshell component in accordance with embodiments of the disclosure;

FIG. 7B is scanning electron microscopy images of capsules of Sample Gin accordance with embodiments of the disclosure, after the processillustrated in FIG. 7A FIG. 8A is scanning electron microscopy images ofcapsules of Sample H with both first and second shell component inaccordance with embodiments of the disclosure;

FIG. 8B is scanning electron microscopy images of a capsule shell ofSample H with both first and second shell component in accordance withembodiments of the disclosure;

FIG. 9 is a scanning electron microcopy image of capsules of ComparativeExample Sample W in accordance with embodiments of the disclosure;

FIG. 10 is an energy dispersive X-ray spectrum of a capsule of Sample Kin accordance with embodiments of the disclosure;

FIG. 11 is an energy dispersive X-ray spectrum of a capsule of Sample AAin accordance with embodiments of the disclosure;

FIG. 12A is an optical microscopy image of capsules of Sample N inaccordance with embodiments of the disclosure prepared using ahydrophilic core;

FIG. 12B is a scanning electron microscopy image of a capsule of SampleN in accordance with embodiments of the disclosure prepared using ahydrophilic core;

FIG. 13 is a graph of the loss percentage of tracer as determined by thepermeability method against to the organic percentage content in thefirst shell component in accordance with embodiments of the disclosure;

FIG. 14 is a graph of mean shell thickness against capsule mean volumeweighted diameter in accordance with embodiments of the disclosure;

FIG. 15A is a scanning electron microscopy image of a capsule shell ofSample B in accordance with embodiments of the disclosure;

FIG. 15B is a scanning electron microscopy image of capsules of Sample Bin accordance with embodiments of the disclosure;

FIG. 16 is a scanning electron microscopy image of a capsule shell ofSample AW in accordance with embodiments of the disclosure;

FIG. 17 is a graph of Degree of Branching against Molecular Weight inaccordance with embodiments of the disclosure;

DETAILED DESCRIPTION

In accordance with embodiments, inorganic capsules having a coresurrounded by a shell are provided. The core can include one or morebenefit agents. In various embodiments, the shell can include a firstshell component and optionally a second shell component that surroundsthe first shell component. In embodiments, the first shell component caninclude a condensed layer formed from the condensation product of aprecursor. As described in detail below, the precursor can include oneor more precursor compounds. In embodiments, the first shell componentcan include a nanoparticle layer. In embodiments, the second shellcomponent can include inorganic materials.

Capsules of this invention are defined as comprising a substantiallyinorganic shell comprising a first shell component and a second shellcomponent. By substantially inorganic it is meant that the first shellcomponent can comprise up to 10 wt %, preferably 9 wt %, preferably 8 wt%, preferably 7 wt %, preferably 6 wt %, preferably 5 wt %, preferably 4wt %, preferably 3 wt %, preferably 2 wt % preferably 1 wt % of organiccontent, as defined later in the organic content calculation and laterin the descriptions. While the first shell component is useful to builda mechanically robust scaffold or skeleton, it can also provide lowshell permeability in liquid products containing surfactants such aslaundry detergents, shower-gels, cleansers, etc . . . (see Surfactantsin Consumer Products, J. Falbe, Springer-Verlag). The second shellcomponent greatly reduces the shell permeability which improves thecapsule impermeability in surfactant-based matrices, as determined bythe shell Permeability Test; (described thereafter).

In the present invention, capsules may be formed by first admixing ahydrophobic material with an inorganic precursor of formula (I),described later, where M is preferably silicon. Said precursor/oilmixture is then either used as a dispersed phase or as a continuousphase in conjunction with a water phase, where in the former case an O/Wemulsion is formed and in the latter a W/O emulsion is formed once thetwo phases are mixed and homogenized via methods that are known to theperson skilled in the art.

In the instance where M is silicon in the inorganic precursor of formula(I), the silica precursor will start undergoing a hydrolysis reactionwith water at the Oil/Water interface to form a partially hydrolyzedprecursor with silanol group(s). Said partially hydrolyzed precursor isthen able to either react with another hydrolyzed precursor to form asiloxane bond, releasing a water molecule or react with an unhydrolyzedprecursor to form also a siloxane bond, releasing an alcohol molecule.The silica precursor can also undergo additional hydrolysis beforereacting with another specie. In addition, the silica precursor canreact with nanoparticles located at the Oil/Water interface, by asimilar mechanism involving either an alcohol or a water releasingcondensation reaction, depending on the state of hydrolysis of saidprecursor. All of the above processes serve to anchor the silicaprecursor at the Oil/Water interface.

The inorganic precursor of formula (I) is characterized by multiplephysical properties, namely a molecular weight (Mw), a degree ofbranching (DB) and a polydispersity index (PDI) of the molecular weightdistribution. It has been found that Mw and DB are important to obtaincapsules that hold their mechanical integrity once left drying on asurface and that have low shell permeability in surfactant-basedmatrices.

Without wishing to be bound by theory, it is believed that by anchoringinorganic precursors of formula (I) to the interface so neatly, a lowwater environment is provided, which has structural impacts on theresulting shell. Such a low water environment will lead to aconsiderably slower reaction time than if monomeric precursors or low Mwoligomers were used, due to a limited contact between the reactingspecies (i.e. water and precursor). In this invention we have overcomethese drawbacks by carefully selecting both the type of precursor usedand nanoparticles, leading to the formation of a dense capsule shell.Without being limited to theory it is believed that upon hydrolysis,inorganic precursors with a low Mw are not interfacially active enoughto start forming the first shell component, and thus a large fractiondisperses into the aqueous phase, reducing the final yield of the shellformation. Once a shell has started to form, inorganic precursors with alow Mw can still diffuse through the forming shell further reducing thedesired yield of the shell. In addition, inorganic precursors with a toosmall degree of branching have fractal dimensions such that they wouldbe mutually transparent towards each other (Applied Catalysis A, vol 96,pp 103, 1993), meaning that two precursors with low Mw and low DB areless likely to react with each other to form a solid shell, eitherleaving voids in the shell or resulting in loss of the precursors to theaqueous phase. If a higher concentration of inorganic precursor is usedto compensate such loss, the water phase will contain too much inorganicprecursor and eventually the whole system will gel. Finally, inorganicprecursors immersed in excess water (i.e. dispersed in water) tend toreact faster, and lead to fast growth of ever larger polymers andparticles. As has been explained above, larger polymers and particleshave limited interpenetration into an existing network and thereforewould not increase the yield of the shell or at the very least notprovide a dense enough shell.

Therefore, to obtain capsules according to the present invention,capsules having a dense and strong shell characterized by low shellpermeability in surfactant based matrices and the ability for mechanicalself-integrity, precursors having a degree of branching above 0.19,preferably above 0.2 and a molecular weight above 600 Da, preferablyabove 700 Da, preferably above 1000 Da are necessary.

In certain embodiments, a mixture of precursors comprising a precursorof formula (I) and TBOS can also be used to obtain capsules that providelow shell permeability in surfactant-based matrices and good mechanicalproperties. It has been found, that when used together with a precursorof formula (I), the permeability is reduced versus using only aprecursor of formula (I). This effect is more pronounced for highermolecular weight precursors.

Without being bound by theory, it is believed that the use of TBOSreduces the porosity of the capsule shell, thus leading to a densershell network. It is known from art that the greater the size of thealkoxy chain bound to the Silicon atom, the slower the hydrolysisreaction is. Therefore, it is believed that when the precursor offormula (I) bearing alkoxy moieties that are shorter than the butoxy ofTBOS, the former starts to react first and forms an initial shell. TBOSwill start hydrolyzing at a later stage and will subsequently react inthe only locations where water can still be found, that is the pores ofthe shell, thus ensuring that the overall permeability of the shell isgreatly reduced and leading to lower capsule permeability.

A second shell component has a primary role of reducing shellpermeability. A second shell component can also greatly improve capsulemechanical properties, such as a capsule rupture force and fracturestrength. Without intending to be bound by theory, it is believed that asecond shell component contributes to the densification of the overallshell by depositing a precursor in pores remaining in the first shellcomponent. A second shell component also adds an extra inorganic layeronto the surface of the capsule.

The second shell component comprises inorganic material chosen from thelist of SiO₂, TiO₂, Al₂O₃, ZrO₂, ZnO₂, CaCO₃, Ca₂SiO₄, Fe₂O₃, Fe₃O₄,clay, gold, silver, iron, nickel, and copper, preferably chosen fromSiO₂. In other embodiments, the preferred component is calciumcarbonate. Preferably, the second shell component material is of thesame type of chemistry as the first shell component in order to maximizechemical compatibility. Second shell components made from organicmaterials are known in existing art but differ from the inorganic secondshell components of the present invention, in that second shellcomponents made from organic materials generally do not provide lowpermeability capsule shells or mechanically improved capsules.

Improved capsule mechanical properties provided by use of a second shellcomponent, as disclosed in this invention, can only be achieved incombinations with unique first shell components. Capsules made fromtetraethoxysilane (TEOS) and commercial polyethoxysilanes (e.g. EvonikDynasylan 40), for example, do not provide satisfactory mechanicalproperties when further combined with inorganic second shell components.It is the unique combination of the first shell and second shellcomponents, as disclosed in this invention, that provides both low shellpermeability in surfactant-based matrices and mechanical robustness.

Without desiring to be bound by theory, it is believed that the secondshell component, as disclosed in the present invention has the uniqueproperty of depositing into the first shell component micropores andcovers most of the final capsule surface, thus providing an improvedmechanical robustness of the capsule. Filling of the micropores reducesthe formation of microcracks when the capsule is under stress by highagitation and upon shell drying. A common solution to the formation ofcapsule shell microcracks can be the use of labile spacers in thecapsule shell network, but this requires the introduction of organicmaterials, and these generally greatly increase the shell permeabilityin surfactant-based matrices, such as laundry detergents

In embodiments, the first shell component can include a condensed layerand a nanoparticle layer, wherein the condensed layer is disposedbetween the core and the nanoparticle layer. In embodiments, the firstshell component can include a metal oxide and/or a semi-metal oxide. Inembodiments, the first shell component can include metal, mineral,metal-oxide, and/or semi-metal oxide nanoparticles. In embodiments thenanoparticles can be one or more of SiO₂, TiO₂, Al₂O₃, ZrO₂, ZnO₂,Fe₂O₃, Fe₃O₄, CaCO₃, clay, silver, gold, and copper. The condensed layerand the nanoparticle layer when both present can have the same ordifferent materials. In embodiments, the first shell component isentirely or substantially entirely SiO₂.

In embodiments, the first shell component is entirely inorganic. Inembodiments, the first shell component can include up to 5% by weight ofthe first shell component organic material. For example, the organicmaterial can be present in the precursor and/or the nanoparticles and/oradded as a separate component. In embodiments, the organic material canbe present from unreacted monomers or byproducts of the polymerization.In embodiments, the nanoparticles can include a surface modificationcontaining organic materials. In embodiments, organic material can beadded to the first shell component.

In embodiments, the capsule can further include a second shell componentwherein the second shell component surrounds the first shell component.In embodiments, the second shell component includes one or more of ametal oxide, a semi-metal oxide, a mineral and a metal. In embodimentsthe second shell component can include one or more of SiO₂, TiO₂, Al₂O₃,ZrO₂, ZnO₂, CaCO₃, Ca₂SiO₄, Fe₂O₃, Fe₃O₄, clay, gold, silver, iron,nickel, and copper. In embodiments, the second shell component isentirely or substantially entirely SiO₂.

In embodiments, the shell only includes the first shell component. Inother embodiments, the shell includes both the first and the secondshell component. In embodiments, the first shell component and thesecond shell component are entirely or substantially entirely SiO₂. Itis also contemplated herein that the shell can include additional shellcomponents. In various embodiments, the core can be an oil-based core.In other embodiments, the core can be a water-based core.

Capsules of the present invention comprise certain physical parameters,such as shell thickness and capsule diameter. The combination andpresence of the unique constraints on capsule size, shell thickness andeffective core/shell ratio leading to the low permeability of the shellis the corner stone of this invention. Not only are each of these valuesindividually important, but also their ratio (i.e. core/shell ratio).For example, shells that are too thin compared to the overall size ofthe capsule tend suffer from a lack of self-integrity and collapse oncedeposited and dried on a surface. On the other hand, shells that areextremely thick as compared to the diameter of the capsule tend to haveincreased shell permeability in a surfactant-based matrix. While it maybe thought that a thick shell leads to low shell permeability (sincethis parameter impacts the overall diffusion pathway across the shell),it has surprisingly been found that capsules having a shell with athickness above a certain threshold have higher shell permeability. Thisdiscovery is in contrast to what is known in the prior art wherein it isbelieved increased shell thickness provides low shell permeability; thecapsules of the present invention demonstrate the teachings of the priorart do not always apply in regard to shell thickness and shellpermeability.

Without being bound by theory, it is believed that in order to increasethe shell thickness of the capsules, two options present themselves:First option, for the same amount of precursor, trying to obtain athicker shell could lead to a porous shell, and therefore result in acapsule having a low shell permeability in a surfactant-based matrix;Second option, increasing the amount of precursor in the core prior tothe emulsification step. In this second scenario, the thickness of thefirst shell component will increase as the reaction is progressing.However, at a certain point the shell becomes so dense due to theadvancement of the reaction that the remaining precursors are unable toenter into contact with the water phase to hydrolyze, hence limitingfurther the increase of shell thickness. This thickness is an upperthreshold. Therefore, capsules with thick first shell components areobtained with a porous shell that is not dense enough to stop furtherreaction with external water from happening. It has been found that thecapsules of this invention cannot increase the thickness of the firstshell component above said upper threshold without it also beingpermeable. However, the upper thickness threshold increases as thecapsule diameter increases.

For capsules containing a core material to perform and be cost effectivein consumer good applications, such as liquid detergent or liquid fabricsoftener, they should: i) be resistant to core diffusion during theshelf life of the liquid product; ii) have ability to deposit on thetargeted surface during application (e.g. washing machine cycle) andiii) be able to release the core material by mechanical shell rupture atthe right time and place to provide the intended benefit for the endconsumer.

The size of a capsule is known to have a critical impact on theefficiency of capture and deposition of capsules on targeted substrates,such as fabrics or hairs. A certain minimum capsule size is neededmaximize their capture when passing through a fabric fiber mesh or hairbundles. When capsules are too large however, they are noticeable eitherby an unpleasant grainy feel or simply by the naked eye.

Shell thickness is usually selected as a compromise between providinglow shell permeability and mechanical strength. Indeed, thin shells canlead to somewhat poor barrier properties against the diffusion of smallvolatile molecules through the capsule shell, such as perfume rawmaterials. However, thick shells provide good barrier properties but atthe expense of lower payload of core-materials, drastically increasingthe encapsulation cost to deliver a certain amount of core materialcompared to a thinner shell. This is particularly a problem forinorganic shells obtained by sol-gel precursors, as those experience adrastic weight loss during the hydrolysis reaction. For instance, shellsobtained from a tetraethoxysilane (TEOS) precursor directly or via apolyalkoxysilane (PAOS) oligomer as an intermediate reactant, will lose72% of initial TEOS weight by the hydrolysis of hydrolysable ethoxymoieties. To overcome these inherent weight losses, one would have toincrease the amount of precursor by more than 3 times to achieve atarget shell thickness, unavoidably increasing the cost of required rawmaterial.

The mechanism of the shell formation of the present invention can bedescribed as “brick and mortar”. More specifically, the first shellcomponent composed of high molecular weight polyalkoxysilane (PAOS)compound and, optionally of nanoparticles, act as the “bricks”,providing structural integrity and mechanical resistance of the capsuleshell. The second shell component composed of a low molecular weightcompound will diffuse within the interstitial space between the bricks,acting as mortar to further increase the mechanical strength of theshell and drastically reduce the shell permeability.

In embodiments, the capsule shells advantageously have low permeability,which advantageously allows for slow diffusion of the encapsulatedbenefit agent when incorporated into a formulated product. Inembodiments, capsules can have improved storage stability, for example,demonstrating reduced shell permeability and slow diffusion of theencapsulated benefit agent over storage time. Without intending to bebound by theory, it is believed that capsule shells in accordance withembodiments of the disclosure have low porosity and high density,thereby enhancing the stability of the capsules as compared toconventional inorganic capsules. Further, without intending to be boundby theory, it is believed that the improved shell architecture allowsfor targeted fracture strengths to be achieved allowing ultimatefracture at the targeted pressure during use. That is, despite increaseddensity and structural stability, the capsules remain capable ofperforming as intended and fracturing at the desired and intendedpressures during use.

Permeability as measured by the Permeability Test Method described belowcorrelates to the porosity of the capsule shells. In embodiments, thecapsules or populations of capsules have a permeability as measured bythe Permeability Test Method of about 0.01% to about 80%, about 0.01% toabout 70%, about 0.01% to about 60%, about 0.01% to about 50%, about0.01% to about 40%, about 0.01% to about 30%, or about 0.01% to about20%. For example, the permeability can be about 0.01, 0.1, 0.5, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, or 80%.

In accordance with embodiments, the capsules or population of capsulescan have a mean volume weighted capsule diameter of at least 10micrometers, a mean shell thickness of at least 170 nm, and acoefficient of variation of capsules diameter of less than or equal to40%. In embodiments the capsules have a liquid core at room temperature.

In variations of the embodiments described herein, the capsules can havea mean shell thickness of about 10 nm to about 10,000 nm, about 10 nm toabout 1000 nm, about 170 nm to 10,000 nm, about 170 nm to about 1000 nm,about 300 nm to about 1000 nm. In embodiments, the shell can have athickness of about 50 nm to about 1000 nm, about 10 nm to about 200 nm,about 100 nm to about 1000 nm, about 200 nm to about 1000 nm, about 300nm to about 1000 nm, about 300 nm to about 800 nm, about 300 to about700 nm, about 300 nm to about 500 nm, or about 300 nm to about 400 nm.For example, the shell thickness can be about 10, 20, 30, 40, 50, 60,70, 80, 90100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375,400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725,750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 2000, 3000,4000, 5000, 6000, 7000, 8000, 9000, or 10,000 nm.

In various embodiments described herein, the capsules can have a meanvolume weighted capsule diameter of about 0.1 micrometers to about 300micrometers, about 0.1 micrometers to about 100 micrometers, about 10micrometers to about 200 micrometers, about 10 micrometers to about 100micrometers, about 10 micrometers to about 75 micrometers, about 50micrometers to about 100 micrometers, or about 10 micrometers to about50 micrometers. Other suitable mean volume weighted capsule diameter ofabout 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 85, 90, 95, 100, 125, 150, 175, 200, 225, 250, 275, or 300micrometers.

In various embodiments, a population of capsules having a large meandiameter can be provided. For example, in various embodiments capsuleshaving a mean diameter of 10 μm or greater or 12 μm or greater can beprovided. In various embodiments, a population of capsules can have amean diameter of the capsules of the population greater than 10 μm. Invarious embodiments, a population of capsules having 60%, 70%, 80%, 90%,and up to 100% of the capsules having a diameter of greater than 10 μmcan be provided. Large capsule diameters can be advantageous to containmore benefit agent, thereby allowing for increased concentration ofbenefit agent in a formulated product without requiring a significantconcentration of capsules. It has been advantageously found that largecapsules can be provided in accordance with embodiments herein withoutsacrificing the stability of the capsules as a whole and/or whilemaintaining good fracture strength.

In embodiments, the capsules can have a value of mean shell thicknessdivided by mean diameter of greater than about 0.1%. In embodiments, thecapsules can have a value of mean shell thickness divided by meandiameter of greater than about 0.2%, or greater than about 0.5%, orgreater than about 1%. For example, the capsules can have a value ofmean shell thickness divided by mean diameter of greater than about 0.2%to about 10%, or 0.2% to about 9%, or about 0.2% to about 7.8%, or about0.2% to about 6%, or about 0.2% to about 5.6%, or about 0.5% to about5.6%.

It has surprisingly been found that in addition to the inorganic shellthe volumetric core-shell ratio plays an important role to ensure thephysical integrity of the capsules. Shells that are too thin vs. theoverall size of the capsule (core:shell ratio >98:02) tend to sufferfrom a lack of self-integrity and collapse once deposited and dried on asurface. On the other hand, shells that are extremely thick vs. thediameter of the capsule (core:shell ratio <80:20) tend to have highershell permeability in a surfactant-rich matrix. While one mightintuitively think that a thick shell leads to lower shell permeability(since this parameter impacts the mean diffusion path of the activeacross the shell), it has surprisingly been found that the capsules ofthis invention that have a shell with a thickness above a threshold havehigher shell permeability. This upper threshold is dependent on thecapsule diameter.

An effective and inventive core:shell ratio is obtained by selecting thecomposition of shell precursor to core material. When the core:shellratio is too low, the large amount of first shell material often leadsto gelling the core, which negatively impacts the migration of shellmaterial at the oil/water interface by disrupting the brick and mortarmechanism. When the core-shell ratio is too large, mechanical strengthprovided by the thin shell is not enough to sustain the core weight upondrying on substrates.

In embodiments, the capsules can have a mean effective volumetriccore-shell ratio of about 60:40 to about 99:1, about 70:30 to about99:1, about 80:20 to about 99:1, 60:40 to about 98:2, about 70:30 toabout 98:2, about 80:20 to about 98:2, about 70:30 to about 96:4, about80:20 to about 96:4, about 90:10 to about 96:4. For example, the meaneffective volumetric core-shell ratio can be about 60:40, 65:35, 70:30,75:25, 80:20, 85:15, 90:10, 95:5, 98:2, or 99:1 and any combinationsthereof.

In embodiments, the capsules can have a mean effective volumetriccore-shell ratio of about 99:1 to about 50:50, a have a mean volumeweighted capsule diameter of about 0.1 μm to about 200 μm, and a meanshell thickness of about 10 nm to about 10,000 nm. In embodiments, thecapsules can have a mean effective volumetric core-shell ratio of about99:1 to about 50:50, a have a mean volume weighted capsule diameter ofabout 10 μm to about 200 μm, and a mean shell thickness of about 170 nmto about 10,000 nm. In embodiments, the capsules can have a meaneffective volumetric core-shell ratio of about 98:2 to about 70:30, ahave a mean volume weighted capsule diameter of about 10 μm to about 100μm, and a mean shell thickness of about 300 nm to about 1000 nm.

In embodiments, the capsules can have a weight core-shell ratio of about60 to 40 to about 99 to 1, about 70 to 30, about 80 to 20, about 70 to30 to about 96 to 4, about 80 to 20 to about 96 to 4, about 90 to 10 toabout 96 to 4. For example, the weight core-shell ratio can be about60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 98:2, or 99:1.

In embodiments, methods in accordance with embodiments of the disclosurecan produce capsule having a low coefficient of variation of capsulediameter. In embodiments, a population of capsules can have acoefficient of variation of capsule diameter of 50% or less, 40% orless, 30% or less, or 20% or less. For example, the coefficient ofvariation of capsule diameter can be less than or equal to 20, 21, 22,23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40,41, 42, 43, 44, 45, 46, 47, 48, 49, or 50%. Control over thedistribution of size of the capsules can beneficially allow for thepopulation to have improved and more uniform fracture strength.Additionally, in embodiments, the fracture strength can be tailored moreeffectively with variation of parameters such as shell thickness, corematerial, because the effect of capsule size is limited over thepopulation by virtue of the narrow distribution of size.

In embodiments, the capsules herein can have an average fracturestrength of at least 0.1 MPa, or at least 0.25 MPa, or about 0.1 MPa toabout 10 MPa, or about 0.25 MPa to about 10 MPa, or about 0.1 MPa toabout 5 MPa, or about 0.25 MPa to about 5 MPa, or about 0.1 MPa to about3 MPa, or about 0.25 MPa to about 3 MPa. For example, the averagefracture strength can be about 0.1 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.4MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, 1.1 MPa, 1.2MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2MPa, 3 MPa, 4 MPa, or 5 MPa. Fully inorganic capsules, such as certainembodiments herein, have traditionally had poor fracture strength,whereas herein, the fracture strength of the capsules can be greaterthan 0.25 MPa providing for improved stability and a triggered releaseof the benefit agent upon a designated amount of rupture stress.

In various embodiments, the capsules can have their mechanicalproperties defined in terms of a parameter of nominal wall tension,which is tension or stretch of capsule wall at rupture. Nominal walltension values are independent of capsules size (Wang et al., “Modellingthe mechanical properties of single suspension-cultured tomato cells”,Annals of Botany, vol. 93, no. 4, pp. 443-453, 2004). Due to such uniquecharacteristics, nominal wall tension can be used to compare themechanical properties of capsules across different mean sizes. Thenominal wall tension, T_(R), is calculated using the method described in“Liu, M. (2010). Understanding the mechanical strength of microcapsulesand their adhesion on fabric surfaces. Birmingham, United Kingdom:University of Birmingham (Doctoral thesis)”.

In accordance with embodiments, capsules can have an average nominalwall tension of at least 0.1 N/m, or at least 0.25 N/m, or about 0.1 N/mto about 20 N/m, or about 0.25 N/m to about 20 N/m, or about 0.5 N/m toabout 20 N/m, or about 0.5 N/m to about 15 N/m, or about 1 N/m to about15 N/m. For example, the average nominal wall tension can be about 0.1N/m, 0.2 N/m, 0.3 N/m, 0.4 N/m, 0.5 N/m, 0.6 N/m, 0.7 N/m, 0.8 N/m, 0.9N/m, 1 N/m, 1.1 N/m, 1.2 N/m, 1.3 N/m, 1.4 N/m, 1.5 N/m, 1.6 N/m, 1.7N/m, 1.8 N/m, 1.9 N/m, 2 N/m, 3 N/m, 4 N/m, 5 N/m, 6 N/m, 7 N/m, 8 N/m,9 N/m, 10 N/m, 11 N/m, 12 N/m, 13 N/m, 14 N/m, or 15 N/m.

In accordance with embodiments, capsules can be made by employing aPickering emulsifier.

The capsules of the present invention comprise a shell surrounding acore, wherein the shell comprises a first shell component and optionallya second shell component. In some embodiments, the first shell componentcomprises nanoparticles, which are preferably of the same chemistry typeas the first shell component formed by the hydrolysis and condensationreaction of the precursors of formula (I).

While it is possible to make capsules of the present invention withoutthe use of nanoparticles due to the good interfacial activity of theprecursor of formula (I), the use of nanoparticles impacts the shellformation mechanism in a way that leads to a more compact layer ofcondensed precursors of formula (I), for reasons detailed below.

In embodiments, the method of making oil-based core containing capsulescan include the use of hydrophilic nanoparticles as Pickeringemulsifiers. According to the literature (Langrnuir 2013, 29, 49,15457-15462) the use of nanoparticles that do not strongly adhere to theemulsion interface (in this case hydrophilic nanoparticles) can providea fine-tuned emulsion process, in which the detachment energy needed toremove the nanoparticles from the interface is minimal. Withoutintending to be bound by theory, it is believed that this allows for theformation of a thicker condensed layer, and the nanoparticles move fromthe water-oil interface to the water-hydrolyzed precursor interface(FIG. 1A), the water-hydrolyzed precursor interface is morethermodynamically favorable as the precursor starts to hydrolyze andbecomes less hydrophobic. The hydrophilic nanoparticles preferentiallyadhere onto the newly formed water-hydrophilic precursor interface. Thehydrolyzed precursor then condensates forming a solid first shellcomponent.

In embodiments, capsules having an oil-based core can be made byadmixing an oil phase with an aqueous phase and emulsifying theadmixture under conditions sufficient to disperse droplets of oil phasein aqueous phase. The oil phase can include an oil-based core modifierand/or oil-soluble benefit agent and a precursor. The aqueous phase caninclude water and nanoparticles. The aqueous phase can further includean acid in embodiments. Upon emulsification, the nanoparticles from theaqueous phase self-assemble around the oil droplets and interpose at theinterface between the continuous aqueous phase and the dispersed oilphase, thereby stabilizing the emulsion and defining the nanoparticlelayer. Further, the precursor present in the oil droplets undergoeshydrolysis and condensation at the interface between the continuouswater phase and the dispersed oil phase between the nanoparticle layerand the oil droplet. The method then further includes curing theemulsions under conditions to further solidify the hydrolyzed andcondensed precursor to thereby form a condensed layer. The nanoparticlelayer and the condensed layer thereby form the first shell component ofthe shell. Without intending to be bound by theory, it is believed thatcovalent bonds are formed between the condensed precursor and thenanoparticles.

In embodiments, capsules having an aqueous-based core can be made byadmixing an aqueous phase with an oil phase and emulsifying theadmixture under conditions sufficient to disperse droplets of aqueousphase in oil phase. The aqueous phase can include an aqueous-basedand/or aqueous-soluble benefit agent. The oil phase can include aprecursor. One or both of the aqueous phase and the oil phase caninclude nanoparticles. Upon emulsification, the nanoparticlesself-assemble around the aqueous droplets and interpose at the interfacebetween the dispersed aqueous phase and the continuous oil phase,thereby defining the nanoparticle layer. Further, the precursor presentin the continuous oil phase undergoes hydrolysis and condensates at theinterface between the continuous oil phase and the dispersed aqueousphase. The method then further includes curing the emulsions underconditions to solidify the hydrolyzed and condensed precursor to therebyform a condensed layer. The nanoparticle layer and the condensed layerthereby form the first shell component of the shell. Without intendingto be bound by theory, it is believed that covalent bonds are formedbetween the condensed precursor and the nanoparticles.

In embodiments, the method, whether including a water-based core or anoil-based core, can further include forming the second shell componentsurrounding the first shell component by admixing the capsules with asolution having second shell component precursors under conditionssufficient to form a second shell component on top of and intimatelyconnected to the capsule first shell component. The solution havingsecond shell component precursors can include a water soluble or oilsoluble precursor. As described above, the second shell component can beinorganic.

In embodiments, the method can further include washing and drying thecapsules after the process of forming the second shell component, usingany suitable methods. For example, centrifugation can be used in awashing step. Drying methods are known in the art. One example of dryingcan be spray drying.

In embodiments, the method of making oil-based core containing capsulescan include the use of hydrophilic nanoparticles as Pickeringemulsifiers. Without intending to be bound by theory, it is believedthat the use of hydrophilic nanoparticles can provide a fine tunedemulsion process, in which, the nanoparticles are not strongly adheredto the emulsion interface, so the detachment energy to remove thenanoparticles from the interface is low. Without intending to be boundby theory, it is believed that this allows for the formation of athicker condensed layer, and the nanoparticles move from the water-oilinterface, to the water-precursor interface (FIG. 1A), the secondinterface is more thermodynamically favorable as the precursor starts tohydrolyze and becomes less hydrophobic. The hydrophilic nanoparticlespreferentially adhere onto the newly formed water-hydrophilic precursorinterface. The hydrolyzed precursor then condensates forming a solidfirst shell component.

In embodiments, the result of the methods herein is a slurry containingthe capsules. In embodiments, the slurry can be formulated into aproduct, such as a consumer product. The formulated product can includein addition to the slurry one or more processing aids. In embodiments,the processing aids can include one or more of water, aggregateinhibiting materials such as divalent salts, and particle suspendingpolymers. In embodiments, the aggregate inhibiting materials can includesalts that can have a charge-shielding effect around the capsule, suchas magnesium chloride, calcium chloride, magnesium bromide, andmagnesium sulfate. In embodiments, formulated product can furtherinclude one or more of xanthan gum, carrageenan gum, guar gum, shellac,alginates, chitosan; cellulosic materials such as carboxymethylcellulose, hydroxypropyl methyl cellulose, cationic cellulosicmaterials; polyacrylic acid; polyvinyl alcohol; hydrogenated castor oil;and ethylene glycol distearate. In embodiments, the formulated productcan include one or more carriers. In embodiments, the carriers can beone or more polar solvents, including but not limited to, water,ethylene glycol, propylene glycol, polyethylene glycol, and glycerol;and nonpolar solvents, including but not limited to, mineral oil,perfume raw materials, silicone oils, and hydrocarbon paraffin oils. Inembodiments, the formulated product can include one or more of silica,citric acid, sodium carbonate, sodium sulfate, sodium chloride, andbinders such as sodium silicates, modified celluloses, polyethyleneglycols, polyacrylates, polyacrylic acids, and zeolites.

Capsules of the present invention can be formed from polyalkoxysilane(PAOS) or polyalkoxysilanes bearing non-hydrolysable moieties. Thoselater PAOS yield capsules with residual organic moieties in the shell.It has been found that capsules with residual organic moieties in theshell present a significantly higher shell permeability compared tocapsules without residual organic moieties. The addition of a secondshell component formation step reduces the shell permeability ofcapsules, thereby allowing a certain quantity of organic moieties intothe first shell component without increasing too much shellpermeability. The primary purpose of PAOS is to produce capsules that donot collapse and have good mechanical properties, while also providing alow shell permeability. Further, comparative testing, as shown below,demonstrates shell permeability is reduced when capsules are producedusing PAOS and not organo-silanes.

In some embodiments, the capsules comprise only the first shellcomponent comprising a condensation product of a precursor of formula(I). These capsules can provide the same or similar benefits as those ofthe present invention comprising a first and second shell component thatis low shell permeability in a surfactant-based matrix and the abilityto hold their integrity when left drying on a surface. However, theshell permeability is greatly reduced when both first and second shellcomponents are included, which is a preferred embodiment of thisinvention.

In certain embodiments, capsules comprise a first shell componentcomprising condensation products of formula (II) precursors (i.e.organosilanes), or mixtures of formula (I) or (II) and monomers bearingone, two, or three carbon silicon bonds.

In addition, when capsules include both a first shell componentcomprising the condensation product of a precursor of formula (II) or amixture of a precursor of formula (I) or (II) and monomers bearing one,two or three carbon silicon bonds, and a second shell component, theshell permeability in a surfactant-based matrix is greatly reduced whencompared to the same capsules lacking a second shell component.

Therefore, whilst capsules comprising a first shell component and asecond shell component, where the first shell component comprisescondensation products of a precursor of Formula (I), are a preferredembodiment, it has been found that the first shell component cantolerate a fraction of condensation products of a precursor of formula(II), or a mixture of precursors of formula (I) or (II), and monomersbearing one, two or three silicon carbon bonds, without complete loss ofpermeability resistance in a surfactant based matrix in the resultantcapsules.

The fraction of condensation products of a precursor of formula (II) isdefined as leading to a total first shell composition comprising lessthan 10 wt %, preferably less than 9 wt %, preferably less than 8 wt %,preferably less than 7 wt %, preferably less than 6 wt %, preferablyless than 5 wt %, preferably less than 4 wt %, preferably less than 3 wt%, preferably less than 2 wt % preferably less than 1 wt % of organiccontent, as defined in the organic content calculation section.

Without desiring to be bound by theory, it is believed that the organiccompounds can act as spacers within the shell thus reducing thecrosslink density of the first shell component, which in too large ofquantities can provide substantial porosity. First shell components thathave a sufficiently low level of organic compounds therefore can resultin higher shell permeability in surfactant-based matrices while stillcontaining enough capability towards self-integrity when drying on asurface.

As defined earlier, whilst the first shell components can be used as ascaffold or skeleton for the capsule in order to provide mechanicalresistance, while still supplying reduced shell permeability in asurfactant-based matrix in certain embodiments, the inclusion of asecond shell component greatly reduces the shell permeability in asurfactant-based matrix. In embodiments, the precursor includes at leastone compound of formula (I) and/or at least one compound of formula (II)in combination with one or more of tetraethoxysilane (TEOS),tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS),triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS),trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS).

In embodiments, emulsifying the dispersed phase and continuous phase caninclude one or more of a high shear homogenization process, amicrofluidization process, and an ultrasonication process. Inembodiments, the emulsification of the dispersed phase and continuousphase can include a high shear homogenization process. In embodiments,the high shear homogenization process can include one or more mixers,such as an ultraturrax mixer or a vortex mixer. In embodiments, themixer can have a speed of 100 rpm to 20,000 rpm, or 500 rpm to 15,000rpm, or 1000 rpm to 10,000 rpm, or 2000 rpm to 10,000 rpm. For example,the mixer can have a speed of 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm,3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm, 6000 rpm, 7000 rpm,8000 rpm, 9000 rpm, or 10,000 rpm.

In embodiments, the dispersed phase and the continuous phase can beemulsified for about 1 minute to about 2 hours, or about 1 minute toabout 30 minutes, or about 1 minute to about 10 minutes. For example,the emulsification can be 1 minute, 2 minutes, 3 minutes, 4 minutes, 5minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes.

In embodiments, the emulsion can be formed substantially free ofsurfactant. In embodiments, the emulsion being “substantially free” ofsurfactant includes surfactant in an amount of 0.001% w/w or less.

In embodiments, a curing process can be used to solidify the shell. Inembodiments, the curing process can induce condensation of theprecursor. In embodiments, the curing process can be done at roomtemperature or above room temperature. In embodiments, the curingprocess can be done at temperatures above 30° C. For example, the curingprocess can be done at 30° C. to 150° C., 40° C. to 120° C., 50° C. to100° C., 60° C. to 100° C., 70° C. to 100° C., or 30° C., 40° C., 50°C., 60° C., 70° C., 75° C., 80° C., 90° C., 100° C., 110° C., 120° C.,130° C., 140° C., or 150° C.

In embodiments, the curing process can be done over any suitable periodof time to enable the capsule shell to be strengthened via condensationof the precursor material. In embodiments, the curing process can bedone over a period of time from 1 minute to 45 days, or 1 minute to 10days, or 1 minute to 5 days, or 1 minute to 24 hours. For example, thecuring process can be done over, 1 minute, 1 hour, 2 hours, 3 hours, 4hours, 5 hours, 6 hours, 12 hours, 24 hours, 48 hours, 72 hours, 96hours, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 15 days, 20days, 21 days, 25 days, 30 days, 35, days 40 days, or 45 days. Longercure times can also be contemplated in the methods described herein.

First Shell Component

In embodiments, the first shell component can include a condensed layer.The condensed layer can be the condensation product of one or moreprecursors. The one or more precursors can be of formula (I):

(M_(v)O_(z)Y_(n))_(w)  (Formula I),

where M is one or more of silicon, titanium and aluminum, v is thevalence number of M and is 3 or 4, z is from 0.5 to 1.6, preferably 0.5to 1.5, each Y is independently selected from —OH, —OR²,

—NH₂, —NHR², —N(R²)₂,

wherein R² is a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ to C₂₂ aryl, ora 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatomsselected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ to C₂₀alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprising from1 to 3 ring heteroatoms selected from O, N, and S, n is from 0.7 to(v-1), and w is from 2 to 2000.

In embodiments, the one or more precursors can be of Formula (I) where Mis silicon. In embodiments, Y is —OR². In embodiments, n is 1 to 3. Inembodiments, Y is —OR₂ and n is 1 to 3. In embodiments, n is at least 2,one or more of Y is —OR₂ and one or more of Y is —OH. In embodiments,one or more of Y is

In embodiments, R² is C₁ to C₂₀ alkyl. In embodiments, R² is C₆ to C₂₂aryl. In embodiments, R² is one or more of C₁ alkyl, C₂ alkyl, C₃ alkyl,C₄ alkyl, C₅ alkyl, C₆ alkyl, C₇ alkyl, and C₈ alkyl.

In embodiments, R² is C₁ alkyl. In embodiments, R² is C₂ alkyl. Inembodiments, R² is C₃ alkyl. In embodiments, R² is C₄ alkyl.

In embodiments, z is from 0.5 to 1.3, or from 0.5 to 1.1, 0.5 to 0.9, orfrom 0.7 to 1.5, or from 0.9 to 1.3, or from 0.7 to 1.3.

In embodiments, M is silicon, v is 4, each Y is —OR², n is 2 and/or 3,and each R² is C₂ alkyl.

In embodiments, the precursor can include polyalkoxysilane (PAOS). Insome embodiments, the precursor can include polyalkoxysilane (PAOS)synthesized via a hydrolytic process.

In embodiments, the precursor can alternatively or further include oneor more of a compound of formula (II):

(M^(v)O_(z)Y_(n)R¹ _(p))_(w)  (Formula II),

where M is one or more of silicon, titanium and aluminum, v is thevalence number of M and is 3 or 4, z is from 0.5 to 1.6, preferably 0.5to 1.5, each Y is independently selected from —OH, —OR²,

—NH₂, —NHR², —N(R²)₂

wherein R² is selected from a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ toC₂₂ aryl, or a 5-12 membered heteroaryl comprising from 1 to 3 ringheteroatoms selected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ toC₂₀ alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprisingfrom 1 to 3 ring heteroatoms selected from O, N, and S, n is from 0 to(v-1), each R¹ is independently selected from a C₁ to C₃₀ alkyl, a C₁ toC₃₀ alkylene, a C₁ to C₃₀ alkyl substituted with one or more of ahalogen, —OCF₃, —NO₂, —CN, —NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino,mercapto, acryloyl, CO₂H, CO₂alkyl, aryl, and heteroaryl, or a C₁ to C₃₀alkylene substituted with one or more of a halogen, —OCF₃, —NO₂, —CN,—NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO₂H,CO₂alkyl, aryl, and heteroaryl, p is present in an amount up to pmax,and w is from 2 to 2000; wherein pmax=60/[9*Mw(R¹)+8], where Mw(R¹) isthe molecular weight of the R group.

In embodiments, R is a C₁ to C₃₀ alkyl substituted with one to fourgroups independently selected from a halogen, —OCF₃, —NO₂, —CN, —NC,—OH, —OCN, —NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO₂H,CO₂alkyl, aryl, and heteroaryl. In embodiments, R is a C₁ to C₃₀alkylene substituted with one to four groups independently selected froma halogen, —OCF₃, —NO₂, —CN, —NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino,mercapto, acryloyl, CO₂H, CO₂alkyl, aryl, and heteroaryl.

In embodiments, the precursor can include at least polyalkoxysilane(PAOS). In embodiments, the precursor can further include one or both oftetraethoxysilane (TEOS), and tetrabutoxysilane (TBOS). In embodiments,the precursor can include polyalkoxysilane (PAOS) synthesized via anon-hydrolytic process. In embodiments, the precursor can include one ormore of compounds of formula (I) and compounds of formula (II), alone orin combination with one or more of tetraethoxysilane (TEOS),tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS),triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS),trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). Inembodiments, the precursor can also include one or more of compounds offormula (I) and formula (II), alone or in combination with one or moreof silane monomers of type Si(YR)_(4-n)R_(n) wherein YR is ahydrolysable group and R is a non-hydrolysable group. Examples of suchmonomers are given earlier in this paragraph, and these are not meant tobe limiting the scope of monomers that can be used.

In embodiments, the compounds of formula (I) and/or the compounds offormula (II) can have a Polystyrene equivalent Weight Average MolecularWeight (Mw) of from about 100 Da to about 300,000 Da. In embodiments,the Mw can be from about 100 Da to about 100,000 Da, or from about 100Da to about 90,000 Da, or from about 100 Da to about 80,000 Da, or fromabout 100 Da to about 70,000 Da, or from about 100 Da to about 60,000about Da, or from about 200 Da to about 60,000 Da, or from about 300 Dato about 60,000 Da, or from about 400 Da to about 60,000 Da, or fromabout 500 Da to about 60,000 Da, or from about 600 Da to about 60,000Da, or from about 700 Da to about 60,000 Da, or from about 700 Da toabout 30,000 Da, or from about 800 Da to about 30,000 Da, or from about900 Da to about 30,000 Da, or from about 1000 Da to about 30,000 Da, orfrom about 1500 Da to about 30,000 Da.

In embodiments, the compounds of formula (I) and/or formula (II) canhave a molecular weight polydispersity index of about 1 to about 50. Inembodiments, the molecular weight polydispersity index can be from about1 to about 45, or about 1 to about 40, or about 1 to about 30 or about 1to about 25, or about 1 to about 20, or about 1 to about 15, or about 1to about 10, or about 1 to about 9, or about 1 to about 8, or about 1 toabout 7, or about 1 to about 6, or about 1 to about 5, or about 1 toabout 4, or about 1.4 to about 5, or about 1.5 to about 3.5. Forexample, the molecular weight polydispersity index can be about 1, 1.1,1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or5.0.

In embodiments, the compounds of formula (I) and/or formula (II) canhave a degree of branching of 0 to about 0.6, about 0.05 to about 0.5,about 0.01 to about 0.1, about 0.03 to about 0.13, about 0.1 to about0.45, or about 0.2 to about 0.3. Other suitable values include about 0,0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2,0.25 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, and 0.6.

In embodiments, the first shell component can further include ananoparticle layer. The nanoparticle of the nanoparticle layer can beone or more of SiO₂, TiO₂, Al₂O₃, ZrO₂, ZnO₂, CaCO₃, clay, silver, gold,and copper. In embodiments, the nanoparticle layer can include SiO₂nanoparticles.

The nanoparticles can have an average diameter of about 1 nm to about500 nm, about 1 nm to 300 nm, about 1 nm to 200 nm, about 5 nm to about100 nm, about 10 nm to about 100 nm, and about 30 nm to about 100 nm.For example, in embodiments, the nanoparticles can have an averagediameter of about 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm,70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm.

In embodiments, the emulsion can advantageously be stabilized by sterichindrance provided by the nanoparticle layer surrounding the droplet andpreventing coalescence. Furthermore, to form emulsions that do notcoalesce, the three-phase contact angle between the nanoparticle and theimmiscible phases should be close to 90°, this is due to the largeradsorption energy for nanoparticles at the oil-water interface resultingin a higher energy input required for desorption, ΔG_(d), according tothe equation:

ΔG _(d) =πr ² γow(1−cos θ)²

where, ΔG_(d) is the free energy, r the nanoparticle radius, yow theinterfacial tension between the oil and water phases and 0 thethree-phase contact angle. The change of free energy of a sphericalnanoparticle at the interface depends directly upon the water-oilinterfacial tension and the radius of the nanoparticle. ΔG_(d) increasesas a function of r², therefore, without intending to be bound by theory,usually bigger nanoparticles can stabilize emulsions more efficientlyand can influence the pore size between nanoparticles.

In embodiments, the pore size can be adjusted by varying the shape ofthe nanoparticles and/or by using a combination of differentnanoparticle sizes. In embodiments, non-spherical irregularnanoparticles can be used as they can have improved packing in formingthe nanoparticle layer, which is believed to yield denser shellstructures. This can be advantageous when limited permeability isrequired. In other embodiments, the nanoparticles used can have moreregular shapes, such as spherical. Any contemplated nanoparticle shapecan be used herein.

In embodiments, the nanoparticles can be substantially free ofhydrophobic modifications. In embodiments, the nanoparticles can besubstantially free of organic compound modifications. In otherembodiments, the nanoparticles can include an organic compoundmodification. In embodiments, the nanoparticles can be hydrophilic.

In embodiments, the nanoparticles can include a surface modificationsuch as but not limited to linear or branched C₁ to C₂₀ alkyl groups,surface amino groups, surface methacrylo groups, surface halogens, orsurface thiols. These surface modifications are such that thenanoparticle surface can have covalently bound organic molecules on it.When it is disclosed in this document that inorganic nanoparticles areused, this is meant to include any of the aforementioned surfacemodifications without being explicitly called out.

Second Shell Component

In embodiments, the capsules can include a second shell component. Thesecond shell component surrounds the first shell component. The secondshell component comprises an inorganic compound. In embodiments, thesecond shell component can provide further stability to the capsules anddecrease the permeability of the capsules. Without intending to be boundby theory, it is believed that the second shell component can furthercontribute to improved performance of the capsules, for example,reducing shell permeability and diffusion of the benefit agent duringstorage.

In embodiments, the second shell component can include one or more of ametal oxide, a semi-metal oxide, a mineral, and a metal. In embodiments,the second shell component can include one or more of SiO₂, TiO₂, Al₂O₃,ZrO₂, ZnO₂, CaCO₃, Ca₂SiO₄, Fe₂O₃, Fe₃O₄, clay, gold, iron, silver,nickel, and copper. In embodiments, the second shell component can besilica. In embodiments, the second shell component can be silica formedfrom mineralized sodium silicate.

In embodiments, the second shell component can include silica formedfrom mineralized sodium silicate. In embodiments, formation of a secondshell component comprising silica can create a denser capsule shell dueto the deposition of silica within the pores of the first shellcomponent. FIG. 10B illustrates an embodiment of a shell having a secondshell component.

In embodiments of the method, the second shell component can be formedby admixing capsules having the first shell component with a solution ofsecond shell component precursor. The solution of second shell componentprecursor can include a water soluble or oil soluble second shellcomponent precursor. In embodiments, the second shell componentprecursor can be one or more of a compound of formula (I) as definedabove, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS),tetrabutoxysilane (TBOS), triethoxymethylsilane (TEMS),diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES), andtetraacetoxysilane (TAcS). In embodiments, the second shell componentprecursor can also include one or more of silane monomers of typeSi(YR)_(4-n)R_(n) wherein YR is a hydrolysable group and R is anon-hydrolysable group. Examples of such monomers are given earlier inthis paragraph, and these are not meant to be limiting the scope ofmonomers that can be used. In embodiments, the second shell componentprecursor can include salts of silicate, titanate, aluminate, zirconateand/or zincate. In embodiments, the second shell component precursor caninclude carbonate and calcium salts. In embodiments, the second shellcomponent precursor can include salts of iron, silver, copper, nickel,and/or gold. In embodiments, the second shell component precursor caninclude zinc, zirconium, Silicon, titanium, and/or aluminum alkoxides.In embodiments, the second shell component precursor can include one ormore of silicate salt solutions such as sodium silicates, silicontetralkoxide solutions, iron sulfate salt and iron nitrate salt,titanium alkoxides solutions, aluminum trialkoxide solutions, zincdialkoxide solutions, zirconium alkoxide solutions, calcium saltsolution, carbonate salt solution. In certain embodiments, a secondshell component comprising CaCO₃ can be obtained from a combined use ofCalcium salts and Carbonate salts. In other embodiments, a second shellcomponent comprising CaCO₃ can be obtained from Calcium salts withoutaddition of carbonate salts, via in-situ generation of carbonate ionsfrom CO₂.

The second shell component precursor can include any suitablecombination of any of the foregoing listed compounds.

In embodiments, the solution of second shell component precursor can beadded dropwise to the capsules. In embodiments, the solution of secondshell component precursor and the capsules can be mixed together forabout 1 hour to about 24 hours, or about 1 hour to about 12 hours, orabout 1 hour to about 5 hours. For example, the solution of second shellcomponent precursor and the capsules can be mixed together for about 1hour, 2 hours, 3 hours, 4 hours, or 5 hours. In embodiments, thesolution of second shell component precursor and the capsules can bemixed together at room temperature or at elevated temperatures, such as30° C. to 60° C., 40° C. to 70° C., 40° C. to 100° C. For example, thesolution of second shell component precursor and the capsules can bemixed together at a temperature of room temperature, 30° C., 35° C., 40°C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 90°C., or 100° C.

In embodiments, the solution of second shell component precursor caninclude the second shell component precursor in an amount of about 1 wt% to about 50 wt % based on the total weight of the solution of secondshell component precursor, or about 1 wt % to about 40 wt %, or about 1wt % to about 30 wt %, or about 1 wt % to about 20 wt %, or about 5 wt %to about 20 wt %. For example, the solution of second shell componentprecursor can include the second shell component precursor in an amountof about 1 wt %, 5 wt %, 10 wt %, 20 wt %, 30 wt %, 40 wt %, or 50 wt %based on the total weight of the solution of second shell componentprecursor.

In embodiment, capsules can be admixed with the solution of second shellcomponent precursor in the presence of an acid. In embodiments, it canbe a weak acid such as HF and acetic acid. In embodiments, the acid canbe a strong acid. In embodiments, the strong acid can include one ormore of HCl, HNO₃, H₂SO₄, HBr, HI, HClO₄, and HClO₃. In embodiments, theacid can include HCl. In embodiments, the concentration of the acid incontinuous solution can be about 0.01 M to about 5 M, or about 0.1 M toabout 5 M, or about 0.1 M to about 2 M, or about 0.1 M to about 1 M. Forexample, the concentration of the acid in the solution of second shellcomponent precursor can be about 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 1 M,1.5 M, 2 M, 3 M, 4 M, or 5 M.

In embodiments, the capsules can be admixed with a solution of secondshell component precursor in the presence of a base. In embodiments, thebase can be one or more of mineral bases, a hydroxide, such as sodiumhydroxide, and ammonia. For example, in embodiments, the base can beabout 10⁻⁵ M to 0.01M NaOH, or about 10⁻⁵ M to about 1M ammonia.

In embodiments, the process of forming a second shell component caninclude a change in pH during the process. For example, the process offorming a second shell component can be initiated at an acidic orneutral pH and then a base can be added during the process to increasethe pH. Alternatively, the process of forming a second shell componentcan be initiated at a basic or neutral pH and then an acid can be addedduring the process to decrease the pH. Still further, the process offorming a second shell component can be initiated at an acid or neutralpH and an acid can be added during the process to further reduce the pH.Yet further the process of forming a second shell component can beinitiated at a basic or neutral pH and a base can be added during theprocess to further increase the pH. Any suitable pH shifts can be used.Further any suitable combinations of acids and bases can be used at anytime in the solution of second shell component precursor to achieve adesired pH. In embodiments, the process of forming a second shellcomponent can include maintaining a stable pH during the process with amaximum deviation of +/−0.5 pH unit. For example, the process of forminga second shell component can be maintained at a basic, acidic or neutralpH. Alternatively, the process of forming a second shell component canbe maintained at a specific pH range by controlling the pH using an acidor a base. Any suitable pH range can be used. Further any suitablecombinations of acids and bases can be used at any time in the solutionof second shell component precursor to keep a stable pH at a desirablerange.

Core

In embodiments, the core, whether oil-based or aqueous, can include oneor more benefit agents, as well as additional components such asexcipients, carriers, diluents, and other agents. In embodiments, thecore can be a liquid core. In embodiments, the core can be a gel core.In embodiments, the core can be aqueous and include a water-based orwater-soluble benefit agent. In embodiments, the core can be oil-basedand can include an oil-based or oil-soluble benefit agent. Inembodiments, the core has a melting point of less than or equal to 15°C. In embodiments, the core is a liquid at the temperature at which itis utilized in a formulated product. In embodiments, the core is liquidat and around room temperature.

Oil-Based Core

An oil-based core is defined as the oil phase present in the core of acore-shell capsule, originating from the emulsification of a dispersedoil phase in a continuous aqueous phase; the aforementioned oil andaqueous phases being substantially immiscible.

In embodiments, the oil-based core, can include about 1 wt % to 100 wt %benefit agent based on the total weight of the core. In embodiments, thecore can include about 25 wt % to 100 wt % benefit agent based on thetotal weight of the core or about 50 wt % to 100 wt % benefit agentbased on the total weight of the core. For example, the core can includea benefit agent based on the total weight of the core of about 55 wt %,60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %,and 100 wt %. In embodiments, the core can include about 80 wt % to 100wt % benefit agent based on the total weight of the core. For example,the benefit agent can be 90 wt %, 91 wt %, 92 wt %, 93 wt %, 94 wt %, 96wt %, 97 wt %, 98 wt %, or 99 wt % of the core based on the total weightof the core.

In embodiments, the oil-soluble and/or oil based benefit agent caninclude one or more of chromogens and dyes, perfume composition, perfumeraw materials, lubricants, silicone oils, waxes, hydrocarbons, higherfatty acids, essential oils, lipids, skin coolants, vitamins,sunscreens, antioxidants, catalysts, malodor reducing agents,odor-controlling materials, softening agents, insect and moth repellingagents, colorants, pigments, pharmaceuticals, pharmaceutical oils,adhesives, bodying agents, drape and form control agents, smoothnessagents, wrinkle control agents, sanitization agents, disinfectingagents, germ control agents, mold control agents, mildew control agents,antiviral agents, drying agents, stain resistance agents, soil releaseagents, fabric refreshing agents and freshness extending agents,chlorine bleach odor control agents, dye fixatives, color maintenanceagents, color restoration/rejuvenation agents, anti-fading agents,anti-abrasion agents, wear resistance agents, fabric integrity agents,anti-wear agents, anti-pilling agents, defoamers, anti-foaming agents,UV protection agents, sun fade inhibitors, anti-allergenic agents,fabric comfort agents, shrinkage resistance agents, stretch resistanceagents, stretch recovery agents, skin care agents, and natural actives,dyes, phase change materials, fertilizers, nutrients, and herbicides.

In embodiments, the oil-based core can include fragrance oil.

In embodiments, the oil-based and/or oil-soluble benefit agent caninclude a perfume or a perfume composition. In embodiments, the perfumecomposition can include one or more of perfume raw materials, essentialoils, malodour reducing agents, and odour controlling agents.

In various embodiments, the perfume composition can include one or moreperfume raw materials. In embodiments, the perfume composition caninclude, by weight based on the total weight of the perfume composition,a combination of or individually (1) about 2.5% to about 30%, or about5% to about 30%, of perfume raw materials characterized by a log P ofless than 3.0 and a boiling point of less than 250° C.; (2) about 5% toabout 30%, or about 7% to about 25%, of perfume raw materialcharacterized by a log P of less than or equal to 3.0 and a boilingpoint greater than or equal to 250° C.; (3) about 35% to about 60%, orabout 40% to about 55%, of perfume raw materials characterized by havinga log P of greater than 3.0 and a boiling point of less than 250° C.;and (4) about 10% to about 45%, or about 12% to about 40%, of perfumeraw materials characterized by having a log P greater than 3.0 and aboiling point greater than 250° C.

In embodiments, the benefit agent can have an average log P of greaterthan or equal to 1.

Water-Based Core

A water-based core is defined as the aqueous phase present in the coreof a core-shell capsule, originating from the emulsification of adispersed aqueous phase in a continuous oil phase; the aforementionedoil and aqueous phases being substantially immiscible.

In embodiments, the water-based core can include about 1 wt % to 99 wt %benefit agent based on the total weight of the core. In embodiments, thecore can include about 1 wt % to 75 wt % benefit agent based on thetotal weight of the core or about 1 wt % to 50 wt % benefit agent basedon the total weight of the core. For example, the core can include abenefit agent based on the total weight of the core of about 1 wt %, 5wt %, 10 wt %, 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45wt %, and 50 wt %. In embodiments, the core can include about 1 wt % to20 wt %, 30 wt % to 50 wt %, or 20 wt % to 40 wt %, benefit agent basedon the total weight of the core.

In embodiments, the water-based and/or water soluble benefit agent isone or more of perfume compositions, perfume raw materials, perfume,skin coolants, vitamins, sunscreens, antioxidants, glycerin, bleachencapsulates, chelating agents, antistatic agents, insect and mothrepelling agents, colorants, antioxidants, sanitization agents,disinfecting agents, germ control agents, mold control agents, mildewcontrol agents, antiviral agents, drying agents, stain resistanceagents, soil release agents, chlorine bleach odor control agents, dyefixatives, dye transfer inhibitors, color maintenance agents, opticalbrighteners, color restoration/rejuvenation agents, anti-fading agents,whiteness enhancers, anti-abrasion agents, wear resistance agents,fabric integrity agents, anti-wear agents, anti-pilling agents,defoamers, anti-foaming agents, UV protection agents, sun fadeinhibitors, anti-allergenic agents, enzymes, water proofing agents,fabric comfort agents, shrinkage resistance agents, stretch resistanceagents, stretch recovery agents, skin care agents, and natural actives,antibacterial actives, antiperspirant actives, cationic polymers, dyes,metal catalysts, non-metal catalysts, activators, pre-formed peroxycarboxylic acids, diacyl peroxides, hydrogen peroxide sources, andenzymes.

In embodiments, the water-based and/or water soluble benefit agent caninclude one or more metal catalysts. In embodiments, the metal catalystcan include one or more ofdichloro-1,4-diethyl-1,4,8,11-tetraaazabicyclo[6.6.2]hexadecanemanganese(II); anddichloro-1,4-dimethyl-1,4,8,11-tetraaazabicyclo[6.6.2]hexadecanemanganese(II). In embodiments, the non-metal catalyst can include one ormore of2-[3-[(2-hexyldodecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;3,4-dihydro-2-[3-[(2-pentylundecyl)oxy]-2-(sulfooxy)propyl]isoquinolinium,inner salt;2-[3-[(2-butyldecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;3,4-dihydro-2-[3-(octadecyloxy)-2-(sulfooxy)propyl]isoquinolinium, innersalt; 2-[3(hexadecyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;3,4-dihydro-2-[2-(sulfooxy)-3-(tetradecyloxy)propyl]isoquinolinium,inner salt; 2-[3-(dodecyloxy)-2-(sulfooxy)propyl]-3,4dihydroisoquinolinium, inner salt;2-[3-[(3-hexyldecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt3,4-dihydro-2-[3-[(2-pentylnonyl)oxy]-2-(sulfooxy)propyl]isoquinolinium,inner salt;3,4-dihydro-2-[3-[(2-propylheptyl)oxy]-2-(sulfooxy)propyl]isoquinolinium,inner salt;2-[3-[(2-butyloctyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;2-[3-(decyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, innersalt; 3,4-dihydro-2-[3-(octyloxy)-2-(sulfooxy)propyl]isoquinolinium,inner salt; and2-[3-[(2-ethylhexyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt.

In embodiments, the water-based and/or water soluble benefit agent caninclude one or more activators. In embodiments, the activator caninclude one or more of tetraacetyl ethylene diamine (TAED);benzoylcaprolactam (BzCL); 4-nitrobenzoylcaprolactam;3-chlorobenzoylcaprolactam; benzoyloxybenzenesulphonate (BOBS);nonanoyloxybenzene-sulphonate (NOBS); phenyl benzoate (PhBz);decanoyloxybenzenesulphonate (C₁₀-OBS); benzoylvalerolactam (BZVL);octanoyloxybenzenesulphonate (C₈-OBS); perhydrolyzable esters;4-[N-(nonaoyl) amino hexanoyloxy]-benzene sulfonate sodium salt(NACA-OBS); dodecanoyloxybenzenesulphonate (LOBS or C₁₂-OBS);10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position); decanoyloxybenzoic acid (DOBA);(6-oclanamidocaproyl)oxybenzenesulfonate; (6-nonanamidocaproyl)oxybenzenesulfonate; and (6-decananidocaproyl)oxybenzenesulfonate.

In embodiments, the water-based and/or water soluble benefit agent caninclude one or more preformed peroxy carboxylic acids. In embodiments,the peroxy carboxylic acids can include one or more ofperoxyrnonosulfuric acids; perimidic acids; percabonic acids;percarboxilic acids and salts of said acids; phthalimidoperoxyhexanoicacid; amidoperoxyacids; 1,12-diperoxydodecanedioic acid; andmonoperoxyphthalic acid (magnesium salt hexahydrate), wherein saidamidoperoxyacids may include N,N′-terephthaloyl-di(6-aminocaproic acid),a monononylamide of either peroxysuccinic acid (NAPSA) or ofperoxyadipic acid (NAPAA), or N-nonanovlaminoperoxycaproic acid (NAPCA).

In embodiments, the water-based and/or water soluble benefit agent caninclude one or more diacyl peroxide. In embodiments, the diacyl peroxidecan include one or more of dinonanoyl peroxide, didecanoyl peroxide,diundecanoyl peroxide, dilauroyl peroxide, and dibenzoyl peroxide,di-(3,5,5-trimethyl hexanoyl) peroxide, wherein said diacyl peroxide canbe clatharated.

In embodiments, the water-based and/or water soluble benefit agent caninclude one or more hydrogen peroxide. In embodiments, hydrogen peroxidesource can include one or more of a perborate, a percarbonate aperoxyhydrate, a peroxide, a persulfate and mixtures thereof, in oneaspect said hydrogen peroxide source may comprise sodium perborate, inone aspect said sodium perborate may comprise a mono- or tetra-hydrate,sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, trisodiumphosphate peroxyhydrate, and sodium peroxide.

In embodiments, the water-based and/or water soluble benefit agent caninclude one or more enzymes. In embodiment, the enzyme can include oneor more of peroxidases, proteases, lipases, phospholipases, cellulases,cellobiohydrolases, cellobiose dehydrogenases, esterases, cutinases,pectinases, man nanases, pectate lyases, keratinases, recductases,oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,tannases, pentosanases, glucanases, arabinosidases, hyaluronidase,chondroitinase, laccases, amnylases, and dnases.

In embodiments, the water-based and/or water-soluble benefit agent caninclude a perfume or a perfume composition. In embodiments, the perfumecomposition can include one or more of perfume raw materials, essentialoils, malodour reducing agents, and odour controlling agents.

In various embodiments, the perfume composition can include one or moreperfume raw materials. In embodiments, the perfume composition caninclude, by weight based on the total weight of the perfume composition,a combination of or individually (1) about 35% to about 60%, or about40% to about 55%, of first perfume raw materials characterized by a logP of less than 1.5 and a boiling point of less than 250° C.; (2) about10% to about 45%, or about 12% to about 40%, of second perfume rawmaterials characterized by a log P of less than or equal to 1.5 and aboiling point greater than or equal to 250° C.; (3) about 2.5% to about30%, or about 5% to about 30%, of third perfume raw materialscharacterized by having a log P of greater than 1.5 and a boiling pointof less than 250° C.; and (4) about 5% to about 30%, or about 7% toabout 25%, of fourth perfume raw materials characterized by having a logP greater than 1.5 and a boiling point greater than 250° C.

In embodiments, the benefit agent can have an average log P less than orequal to 1.

Methods of Making Oil-Based Core Capsules

In embodiments of the method of making capsules having an oil-basedcore, the oil phase can include an oil-based and/or oil-soluble benefitagent and a precursor.

In embodiments, the precursor is present in an amount of about 1 wt % toabout 50 wt % based on the total weight of the oil phase. Other suitableamounts include about 1 wt % to about 15 wt %, about 5 wt % to about 30wt %, about 10 wt % to about 20 wt %, about 15 wt % to about 40 wt %,about 25 wt % to about 45 wt %, or about 15 wt % to about 50 wt %, basedon the total weight of the oil phase. For example, the oil phase caninclude, based on the total weight of the oil phase, about 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26,28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, or 50 wt %.

In embodiments, the oil phase, prior to emulsification, can includeabout 10 wt % to about 99 wt % benefit agent based on the total weightof the oil phase, or about 20 wt % to about 99 wt %, about 40 wt % toabout 99 wt %, or about 50 wt % to about 99 wt %, or about 50 wt % toabout 90 wt %. For example, the benefit agent can be present in anamount based on the total weight of the oil phase of about 10 wt %, 20wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80 wt %, or 90 wt %.

The oil phase can further include one or more oil-solublecore-modifiers. For example, an oil-soluble core modifier can be one ormore of partitioning modifier and/or a density modifier. In embodiments,the partitioning modifier can include oil soluble materials that have alog P greater than about 1, or greater than about 2, or greater thanabout 3, or greater than about 4, or greater than about 5, or greaterthan about 6, or greater than about 7, or greater than about 8, orgreater than about 9, or greater than about 10, or greater than about11. In embodiments, the partitioning modifier can include oil solublematerials with a density of greater than or equal to 1 gram per cubiccentimeter. In embodiments, the partitioning modifier can include one ormore of a mono-ester, di-ester and tri-esters of C₄-C₂₄ fatty acids andglycerine; fatty acid esters of polyglycerol oligomers;polyalphaolefins; silicone oil; crosslinked silicones comprisingpolyether substituted structural units and acrylate crosslinks;polyglycerol ether silicone crosspolymers; alkyl substituted cellulose;hydroxypropyl cellulose; fatty esters of acrylic or methacrylic acidthat have side chain crystallizing groups; copolymers of ethylene,including ethylene and vinyl acetate, ethylene and vinyl alcohol,ethylene/acrylic elastomers; acetyl caryophyllene, hexarose, butyloleate, hydrogenated castor oil, sucrose benzoate, dodecanoic acid,palmitic acid, stearic acid, tetradecanol, hexadecanol, 1-octanediol,isopropyl myristate, castor oil, mineral oil, isoparaffin, caprylictriglyceride, soybean oil, vegetable oil, brominated vegetable oil,bromoheptane, sucrose octaacetate, geranyl palmitate,acetylcaryophyllene, sucrose benzoate, butyl oleate, silicones,polydimethylsiloxane, vitamin E, decamethylcyclopentasiloxane,dodecamethylcyclohxasiloxane, sucrose soyate, sucrose stearate, sucrosesoyanate, lauryl alcohol, 1-tetradecanol, 1-hexadecanol, cetyl alcohol,1-octadecanol, 1-docosanol, 2-octyl-1-dodecanol, perfume oils, in oneaspect perfume oils having a log P>5, in one aspect said perfume oilsmay be selected from the group consisting of: Octadecanoic acid,octadecyl ester; Tetracosane, 2,6,10,15,19,23-hexamethyl-; Octadecanoicacid, diester dissolved in 1,2,3-propanetriol; Isotridecane,1,1′-[(3,7-dimethyl-6-octenylidene)bis(oxy)]bis-; Tetradecanoic acid,octadecyl ester; 2,6,10,14,18,22-Tetracosahexaene,2,6,10,15,19,23-hexamethyl-, (all-E)-; Tricosane; Docosane; Hexadecanoicacid, dodecyl ester; 1,2-Benzenedicarboxylic acid, didodecyl ester;Decanoic acid, 1,2,3-propanetriyl ester; 1-Undecene,11,11-bis[(3,7-dimethyl-6-octenyl)oxy]-; Heneicosane; Benzene,[2-[bis[(3,7-dimethyl-2,6-octadienyl)oxy]methyl]-1-; 1-Undecene,11,11-bis[(3,7-dimethyl-2,6-octadienyl)oxy]-; Benzene,[2-[bis[(1-ethenyl-1,5-dimethyl-4-hexenyl)oxy]methyl]-1-; Dodecanoicacid, tetradecyl ester; 2H-1-Benzopyran-6-ol,3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-,[2R-[2R*(4R*,8R*)]]-; Octanoic acid, octadecyl ester; Eicosane;2H-1-Benzopyran-6-ol,3,4-dihydro-2,5,8-trimethyl-2-(4,8,12-trimethyltridecyl)-,[2R*(4R*,8R*)]-; 2-Naphthalenol,1-[6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methyl-3-hexenyl]decahydro-2,5,5,8a-tetramethyl-,[1R-[1.alpha.[E(S*)],2.beta.,4a.beta.,8a.alpha.]]-;2H-1-Benzopyran-6-ol,3,4-dihydro-2,7,8-trimethyl-2-(4,8,12-trimethyltridecyl)-,[2R-[2R*(4R*,8R*)]]-; Heptanoic acid, octadecyl ester; Nonadecane;2,4,6,8,10,12,14,16-Heptadecaoctaenal,2,6,11,15-tetramethyl-17-(2,6,6-trimethyl-1-cyclohexen-1-yl)-,(2E,4E,6E,8E,10E,12E,14E,16E)-; 2H-1-Benzopyran-6-ol,3,4-dihydro-2,8-dimethyl-2-(4,8,12-trimethyltridecyl)-,[2R-[2R*(4R*,8R*)]]-; Hexadecanoic acid, 2-ethylhexyl ester;1,2-Benzenedicarboxylic acid, didecyl ester; Octadecane; Benzoic acid,2-[[2-(phenylmethylene)octylidene]amino]-,1-ethenyl-1,5-dimethyl-4-hexenylester;Octadecanoic acid, 3-methylbutyl ester; Decanoic acid, ester with1,2,3-propanetriol octanoate; Heptadecane; 1-Hexadecene,7,11,15-trimethyl-3-methylene-; Dodecanoic acid, decyl ester;Octadecanoic acid, butyl ester; Decanedioic acid, bis(2-ethylhexyl)ester; Benzene, [2,2-bis[(3,7-dimethyl-6-octenyl)oxy]ethyl]-; Benzene,[2,2-bis[(3,7-dimethyl-2,6-octadienyl)oxy]ethyl]-; 9-Octadecenoic acid(Z)-, butyl ester; Octanoic acid, 1,2,3-propanetriyl ester; Hexadecane;Cyclohexene,4-(5-methyl-1-methylene-4-hexenyl)-1-(4-methyl-3-pentenyl)-;2-Hexadecen-1-ol, 3,7,11,15-tetramethyl-, acetate,[R-[R*,R*-(E)]]-Hexadecanoic acid, butyl ester; Octadecanoic acid, ethylester; 1-Dodecanol, 2-octyl-; Pentadecane; Tetradecanoic acid, hexylester; Decanoic acid, decyl ester; Acetic acid, octadecyl ester;Hexadecanoic acid, 2-methylpropyl ester; 9-Octadecenoic acid (Z)-, ethylester; Heptadecanoic acid, ethyl ester; Octadecanoic acid, methyl ester;Tetradecane; Tetradecanoic acid, 3-methylbutyl ester; 2-Hexadecen-1-ol,3,7,11,15-tetramethyl-, [R-[R*,R*-(E)]]-; 2-Hexadecen-1-ol,3,7,11,15-tetramethyl-; Hexadecanoic acid, 1-methylethyl ester;1H-Indole, 1,1′-(3,7-dimethyl-6-octenylidene)bis-; Octadecanoic acid;Cyclopentasiloxane, decamethyl-; Benzoic acid,2-[[2-(phenylmethylene)octylidene]amino]-,3-methylbutyl ester;9,12-Octadecadienoic acid (Z,Z)-, ethyl ester; 1-Octadecanol;Hexanedioic acid, dioctyl ester; 9-Octadecenoic acid (Z)-, methyl ester;Octadecanoic acid, 2-hydroxypropyl ester; Tetradecanoic acid, butylester; Dodecanoic acid, hexyl ester; 9,12,15-Octadecatrienoic acid,ethyl ester, (Z,Z,Z)-; Hexadecanoic acid, ethyl ester; 1-Hexadecanol,acetate; 9-Octadecenoic acid (Z)-; Hexanedioic acid, bis(2-ethylhexyl)ester; 1,8,11,14-Heptadecatetraene; 1,8,11,14-Heptadecatetraene;1,8,11,14-Heptadecatetraene; 9-Octadecen-1-ol, (Z)-; Tetradecanoic acid,2-methylpropyl ester; Nonanoic acid, 1-methyl-1,2-ethanediyl ester;Tridecane; Naphthalene, decahydro-1,6-dimethyl-4-(1-methylethyl)-,[1S-(1.alpha.,4.alpha.,4a.alpha.,6.alpha.,8a.beta.)]-, didehydro deriv.;1-Hexadecyn-3-ol, 3,7,11,15-tetramethyl-; 9,12-Octadecadienoic acid(Z,Z)-, methyl ester; 1-Heptadecanol; 6,10,14-Hexadecatrien-3-ol,3,7,11,15-tetramethyl-; Benzoic acid,2-[[[4-(4-methyl-3-pentenyl)-3-cyclohexen-1-yl]methylene]amino]-, methylester; 9,12-Octadecadienoic acid (Z,Z)-; 2-Nonene, 1,1′-oxybis-;Santalol, benzeneacetate; 10-Undecenoic acid, heptyl ester;9,12,15-Octadecatrienoic acid, methyl ester, (Z,Z,Z)-; Octadecanoicacid, monoester with 1,2,3-propanetriol; Dodecanoic acid, pentyl ester;Octanoic acid, nonyl ester; Pentadecanoic acid, ethyl ester;Hexadecanoic acid, methyl ester; Dodecanoic acid, 4-methylphenyl ester;Dodecanoic acid, 3-methylbutyl ester; Tetradecanoic acid, 1-methylethylester; Hexadecanoic acid; 1-Phenanthrenecarboxylic acid,tetradecahydro-1,4a-dimethyl-7-(1-methylethyl)-, methyl ester,[1R-(1.alpha.,4a.beta.,4b.alpha.,7.beta.,8a.beta.,10a.alpha.)]-;1-Hexadecanol; Dodecane; 2-Pentadecanone, 6,10,14-trimethyl-;9-Heptadecanone; 1-Phenanthrenemethanol,1,2,3,4,4a,4b,5,6,10,10a-decahydro-1,4a-dimethyl-7-(1-methylethyl)-,acetate, [1R-(1.alpha.,4a.beta.,4b.alpha.,10a.alpha.)]-; Isohexadecanol;Dodecanoic acid, 2-methylpropyl ester; Hexadecanenitrile; Octadecanoicacid, 2,3-dihydroxypropyl ester; Isododecane; 1-Phenanthrenemethanol,tetradecahydro-1,4a-dimethyl-7-(1-methylethyl)-; Octanoic acid,3,7-dimethyl-2,6-octadienyl ester, (E)-; Dodecanoic acid, butyl ester;Tetradecanoic acid, ethyl ester; Butanoic acid, dodecyl ester; Benzoicacid, 2-amino-, decyl ester; Oxacycloheptadecan-2-one; Propanoic acid,2-methyl-, dodecyl ester; 1H-Indene, octahydro-1,1,2,3,3-pentamethyl-;1-Phenanthrenecarboxylic acid,1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydro-1,4a-dimethyl-7-(1-methylethyl)-,methyl ester; 9-Octadecenoic acid (Z)-, ester with 1,2,3-propanetriol;9,12,15-Octadecatrienoic acid, (Z,Z,Z)-; 1,4,8-Cycloundecatriene,2,6,6,9-tetramethyl-, (E,E,E)-; 1-Phenanthrenemethanol,dodecahydro-1,4a-dimethyl-7-(1-methylethyl)-; Benzoic acid,3,4,5-trihydroxy-, dodecyl ester; 1H-Indole-1-heptanol,.eta.-1H-indol-1-yl-.alpha.,.alpha.,.epsilon.-; Cyclododecane;9-Hexadecenoic acid, (Z)-; Benzoic acid,2-[[2-(phenylmethylene)heptylidene]amino]-, methyl; 9-Octadecenoic acid(Z)-, 2,3-dihydroxypropyl ester; 2-Naphthalenecarboxaldehyde,5,6,7,8-tetrahydro-3,5,5,6,7,8,8-heptamethyl-, trans-; Octanoic acid,1-ethenyl-1,5-dimethyl-4-hexenyl ester; and 2-Hexadecanone.

In embodiments, the density modifiers can include one or more ofbrominated vegetable oil; sucrose octaacetate; bromoheptane; titaniumdioxide; zinc oxides; iron oxides; cobalt oxides; nickel oxides; silveroxides; copper oxides; zirconium oxides; silica; silver; zinc; iron;cobalt; nickel; copper; epoxidized soybean oil polyols; 1h-indene,2,3-dihydro-1,1,3,3,5-pentamethyl-4,6-dinitro-; benzene,(2-bromoethenyl)-; benzeneacetic acid, 2-methoxy-4-(1-propenyl)phenylester; ethanone, 1-(2,5-dimethyl-3-thienyl)-; oxiranecarboxylic acid,3-(4-methoxyphenyl)-, ethyl ester; benzoic acid,2-[(1-hydroxy-3-phenylbutyl)amino]-, methyl ester;1,3-benzodioxole-5-carboxylic acid, ethyl ester; 1,3-benzodioxole,5-(2-propenyl)-; benzoic acid, 4-methoxy-; benzenemethanol,.alpha.-(trichloromethyl)-, acetate; phenol, 2-methoxy-4-(2-propenyl)-,formate; phenol, 2-methoxy-4-(2-propenyl)-, benzoate; 2-propen-1-ol,3-phenyl-, benzoate; benzeneacetic acid, 3-methylphenyl ester; benzene,1-(1,1-dimethylethyl)-3,4,5-trimethyl-2,6-dinitro-; benzeneacetic acid,4-methylphenyl ester; benzeneacetic acid, phenylmethyl ester;benzeneacetic acid, (4-methoxyphenyl)methyl ester; 2-propenoic acid,3-phenyl-, phenylmethyl ester; 2-propenoic acid, 3-phenyl-,2-phenylethyl ester; benzeneacetic acid, 2-methoxy-4-(2-propenyl)phenylester; phenol, 2-(methylthio)-; benzoic acid,2-[[3-(1,3-benzodioxol-5-yl)-2-methylpropylidene]amino]-, methyl ester;benzoic acid, 2-[[3-(4-methoxyphenyl)-2-methylpropylidene]amino]-,methylester; benzoic acid, 3,5-dimethoxy-; benzoic acid, 2-hydroxy-, phenylester; benzoic acid, 2-hydroxy-, phenylmethyl ester; benzoic acid,2-hydroxy-, ethyl ester; benzoic acid, 2-hydroxy-, methyl ester; benzoicacid, 2-amino-, methyl ester; ethanone, 2-hydroxy-1,2-diphenyl-; benzoicacid, 4-hydroxy-, ethyl ester; benzoic acid, phenylmethyl ester;1,3-benzodioxole, 5-(1-propenyl)-; benzothiazole, 2-methyl-;5h-dibenzo[a,d]cyclohepten-5-one, 10,11-dihydro-; oxiranecarboxylicacid, 3-phenyl-, ethyl ester; benzoic acid, 4-methoxy-, methyl ester;2-propenoic acid, 3-phenyl-, 3-phenyl-2-propenyl ester;tricyclo[3.3.1.13,7]decan-2-ol, 4-methyl-8-methylene-;tricyclo[3.3.1.13,7]decan-2-ol, 4-methyl-8-methylene-, acetate;methanone, bis(2,4-dihydroxyphenyl)-; methanone,(2-hydroxy-4-methoxyphenyl)phenyl-; dibenzofuran; benzoic acid,2-amino-, 2-phenylethyl ester; ethanone,1-(naphthalenyl)-;furan,2,2′-[thiobis(methylene)]bis-; 1,2,3-propanetriol, tripropanoate;2-propenoic acid, 3-phenyl-, (e)-; phenol, 4-ethyl-2,6-dimethoxy-;disulfide, methyl phenyl; benzoic acid,2-[[(4-methoxyphenyl)methylene]amino]-, methyl ester; 2-propenoic acid,3-(2-methoxyphenyl)-, (z)-; 8-quinolinol; disulfide, bis(phenylmethyl);1,2-propanediol, dibenzoate; benzene, 1-bromo-4-ethenyl-; trisulfide,di-2-propenyl; phenol, 2,6-dimethoxy-4-(1-propenyl)-, (e)-; benzene,(2-isothiocyanatoethyl)-; benzoic acid, 2-hydroxy-5-methyl-, methylester; 1,2,4-trithiolane, 3,5-dimethyl-; propanoic acid,2-(methyldithio)-, ethyl ester; benzoic acid, 2-hydroxy-, cyclohexylester; benzoic acid, 2-[(1-oxopropyl)amino]-, methyl ester; ethanethioicacid, s-(4,5-dihydro-2-methyl-3-furanyl) ester; benzoic acid,2-(acetylamino)-, methyl ester; 1,3,5-trithiane, 2,4,6-trimethyl-;benzoic acid, 2-amino-, propyl ester; butanoic acid, 1-naphthalenylester; benzoic acid, 2,4-dihydroxy-3-methyl-, methyl ester; trisulfide,methyl 2-propenyl; 2-furanmethanol, benzoate; benzoic acid,2-hydroxy-5-methyl-, ethyl ester; benzene,(2,2-dichloro-1-methylcyclopropyl)-; 2-thiophenecarboxaldehyde,5-ethyl-; benzoic acid, [(phenylmethylene)amino]-, methyl ester;spiro[1,3-dithiolo[4,5-b]furan-2,3′(2′h)-furan],hexahydro-2′,3a-dimethyl-; 1,3-benzodioxole, 5-(diethoxymethyl)-;cyclododeca[c]furan, 1,3,3a,4,5,6,7,8,9,10,11,13a-dodecahydro-;benzeneacetic acid, 2-methoxyphenyl ester; 2-benzofurancarboxaldehyde;1,2,4-trithiane, 3-methyl-; furan, 2,2′-[dithiobis(methylene)]bis-;1,6-heptadiene-3,5-dione, 1,7-bis(4-hydroxy-3-methoxyphenyl)-, (e,e)-;benzoic acid, 2,4-dihydroxy-3,6-dimethyl-, methyl ester; benzoic acid,2-hydroxy-4-methoxy-, methyl ester; propanoic acid, 2-methyl-,1,3-benzodioxol-5-ylmethyl ester; 1,2,4-trithiolane, 3,5-diethyl-;1,2,4-trithiolane, 3,5-bis(1-methylethyl)-; furan,2-[(methyldithio)methyl]-; tetrasulfide, dimethyl; benzeneacetaldehyde,.alpha.-(2-furanylmethylene)-; benzoic acid, 3-methoxy-;benzenecarbothioic acid, s-methyl ester; benzoic acid, 2-methoxy-,methyl ester; benzoic acid, 2-hydroxy-, 4-methylphenyl ester; benzoicacid, 2-hydroxy-, propyl ester; 2-propenoic acid, 3-(2-methoxyphenyl)-;2-propenoic acid, 3-(3-methoxyphenyl)-; benzoic acid,2-hydroxy-4-methoxy-6-methyl-, ethyl ester; benzaldehyde,2-hydroxy-5-methyl-; 1,2,3-propanetriol, tribenzoate; benzoic acid,4-methylphenyl ester; 2-furancarboxylic acid, propyl ester; benzoicacid, 2-hydroxy-, 2-methylphenyl ester; benzoic acid,4-hydroxy-3-methoxy-, ethyl ester; 2-propenoic acid, 3-phenyl-; benzene,1,3-dibromo-2-methoxy-4-methyl-5-nitro-; benzene,(isothiocyanatomethyl)-; 2-propenoic acid, 3-(2-furanyl)-, ethyl ester;benzenemethanethiol, 4-methoxy-; 2-thiophenemethanethiol; benzene,1,1′-[(2-phenylethylidene)bis(oxymethylene)]bis-; phenol,2,6-dimethoxy-4-(2-propenyl)-; benzoic acid,2-[(2-phenylethylidene)amino]-, methyl ester; benzenepropanoic acid,.beta.-oxo-, 4-methylphenyl ester; 1h-indole-3-heptanol,.eta.-1h-indol-3-yl-.alpha.,.alpha.,.epsilon.-trimethyl-; benzoic acid,2-hydroxy-, 3-methyl-2-butenyl ester; 1,3-benzodioxole-5-propanol,.alpha.-methyl-, acetate; thiophene, 2,2′-dithiobis-; benzoic acid,2-hydroxy-; benzaldehyde, 2-hydroxy-4-methyl-; disulfide, methylphenylmethyl; 2-furancarboxylic acid, 2-phenylethyl ester; benzenethiol,2-methoxy-; benzoic acid,2-[[(4-hydroxy-3-methoxyphenyl)methylene]amino]-,methyl ester; ethanol,2-(4-methylphenoxy)-1-(2-phenylethoxy)-; benzeneacetic acid,3-phenyl-2-propenyl ester; benzoic acid, 2-amino-, 2-propenyl ester;bicyclo[3.2.1]octan-8-one, 1,5-dimethyl-, oxime; 2-thiophenethiol;phenol, 2-methoxy-4-(1-propenyl)-, formate; benzoic acid, 2-amino-,cyclohexyl ester; phenol, 4-ethenyl-2-methoxy-; benzoic acid,2-hydroxy-, 2-(1-methylethoxy)ethyl ester; ethanone,1-[4-(1,1-dimethylethyl)-2,6-dimethyl-3,5-dinitrophenyl]-; benzene,1-(1,1-dimethylethyl)-3,5-dimethyl-2,4,6-trinitro-; 2-propenoic acid,3-(4-methoxyphenyl)-; benzene,1-(1,1-dimethylethyl)-2-methoxy-4-methyl-3,5-dinitro-;1,2-benzenedicarboxylic acid, diethyl ester; ethanone,1-(3,4-dihydro-2h-pyrrol-5-yl)-; benzoic acid, 2-(methylamino)-, methylester; 2h-1-benzopyran-2-one, 7-ethoxy-4-methyl-; benzoic acid,2-hydroxy-, 2-phenylethyl ester; benzoic acid, 2-amino-, ethyl ester;2-propen-1-ol, 3-phenyl-, 2-aminobenzoate; phenol,4-chloro-3,5-dimethyl-; disulfide, diphenyl; 1-naphthalenol;[1,1′-biphenyl]-2-ol; benzenemethanol, .alpha.-phenyl-;2-naphthalenethiol; ethanone, 1-(2-naphthalenyl)-; phenol,2-methoxy-4-(1-propenyl)-, acetate; 2-naphthalenol, benzoate; benzoicacid, phenyl ester; pyridine, 2-[3-(2-chlorophenyl)propyl]-; benzoicacid, 4-hydroxy-, propyl ester; ethanone, 1-(1-naphthalenyl)-; propanoicacid, 3-[(2-furanylmethyl)thio]-, ethyl ester; 2-propen-1-one,1,3-diphenyl-; 3-pyridinecarboxylic acid, phenylmethyl ester; benzoicacid, 2-phenylethyl ester; piperidine,1-[5-(1,3-benzodioxol-5-yl)-1-oxo-2,4-pentadienyl]-,(e,e)-; andbenzothiazole.

In embodiments of the method of making capsules having an oil-basedcore, the aqueous phase (continuous phase) can include water, an acid,and nanoparticles. In embodiments, the aqueous phase has a pH of about 1to about 14 at least at the time of admixing with the oil phase. Othersuitable pH include about 1 to about 5, about 2 to about 7, about 6 toabout 7, about 1 to about 4, about 3 to about 7, about 7 to 14, about 8to 10, about 9 to 11, or about 7 to 9. For example, the pH of theaqueous phase can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or14.

In embodiments, the acid can be a strong acid. In embodiments, thestrong acid can include one or more of HCl, HNO₃, H₂SO₄, HBr, HI, HClO₄,and HClO₃. In embodiments, the acid can include HCl. In embodiments, theconcentration of the acid in continuous solution can be about 0.01 M toabout 5 M, or about 0.1 M to about 5 M, or about 0.1 M to about 2 M, orabout 0.1 M to about 1 M. For example, the concentration of acid in thecontinuous solution can be about 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 1 M,1.5 M, 2 M, 3 M, 4 M, or 5 M.

In embodiments, the acid can be a weak acid, such as HF and acetic acid.

In embodiments of the method of making capsules having an oil-basedcore, the aqueous phase (continuous phase) can include a base. Inembodiments, the base can be one or more of mineral bases, a hydroxide,such as sodium hydroxide, and ammonia. For example, in embodiments, thebase can be about 10⁻⁵ M to 0.01M NaOH, or about 10⁻⁵ M to about 1Mammonia.

In embodiments of the method of making capsules having an oil-basedcore, the pH can be varied throughout the process by the addition of anacid and/or a base. For example, the method can be initiated with anaqueous phase at an acidic or neutral pH and then a base can be addedduring the process to increase the pH. Alternatively, the method can beinitiated with an aqueous phase at a basic or neutral pH and then anacid can be added during the process to decrease the pH. Still further,the method can be initiated with an aqueous phase at an acid or neutralpH and an acid can be added during the process to further reduce the pH.Yet further the method can be initiated with an aqueous phase at a basicor neutral pH and a base can be added during the process to furtherincrease the pH. Any suitable pH shifts can be used. Further anysuitable combinations of acids and bases can be used at any time in themethod to achieve a desired pH.

Any of the nanoparticles described above can be used in the aqueousphase. In embodiments, the nanoparticles can be present in an amount ofabout 0.01 wt % to about 10 wt % based on the total weight of theaqueous phase. Other suitable amounts include about 0.05 wt % to about 5wt %, about 1 wt % to about 10 wt %, about 5 wt % to about 8 wt %, about2 wt % to about 7 wt %, or about 0.1 wt % to about 1 wt %. For example,the nanoparticles can be present in an amount based on the total weightof the aqueous phase of about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07,0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5,6, 7, 8, 9, or 10 wt %.

In embodiments, the method can include admixing the oil phase and theaqueous phase in a ratio of oil phase to aqueous phase of about 1:10 toabout 1:1, about 1:9 to about 1:1, about 1:5 to about 1:1, about 1:3 toabout 1:1, about 1:5 to about 1:2, about 1:3 to about 1:1.5. Othersuitable ratios include about 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3,1:2, 2:5, 3:5, 1:1.5, or 1:1.

Methods of Making Aqueous Core Capsules

In embodiments of the method of making capsules having an aqueous core,the aqueous phase can include an aqueous benefit agent.

In embodiments, the aqueous phase, prior to emulsification, can includeabout 1 wt % to about 99 wt % benefit agent based on the total weight ofthe aqueous phase, or about 20 wt % to about 99 wt %, about 40 wt % toabout 99 wt %, or about 50 wt % to about 99 wt %, or about 50 wt % toabout 90 wt %. For example, the benefit agent can be present in anamount based on the total weight of the aqueous phase of about 1 wt %,10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80 wt %,or 90 wt %.

In embodiments, the aqueous phase can further include one or more coremodifiers. For example, an aqueous core modifier can be one or more of apH modifier, viscosity modifier, ionic strength modifiers, aestheticmodifiers, density modifiers, and gelling agents. In embodiments, the pHmodifier may be incorporated to generate the desired pH in the core. Inembodiments, the pH modifier can include any alkali or acid known tothose skilled in the art of detergent manufacture, for example, amongthe alkalis: carbonate and hydroxycarbonate salts of alkaline oralkaline-earth metals, e.g., sodium or potassium hydroxide carbonate;oxides and hydroxides of alkaline or alkaline-earth metals, e.g.,magnesium oxide, sodium or potassium hydroxide; citrate, fumarate,succinate, tartarate, maleate, ascorbate, silicate of alkaline oralkaline-earth metals, e.g., sodium citrate; among the acids: citricacid, fumaric acid, succinic acid, tartaric acid, malic acid, ascorbicacid, phosphoric acid, hydrochloric acid, sulfuric acid, sulforous acid.

In embodiments, the viscosity modifiers can include nanofibrillated andmicrofibrillated cellulose, uncoated or coated with a polymericthickener, of bacterial or vegetable origin; non-polymeric crystalline,hydroxyl functional materials such as a crystallizable glyceride,including hydrogenated castor oil; naturally derived polymericstructurants such as hydroxyethyl cellulose, hydrophobically modifiedhydroxyethyl cellulose, carboxymethyl cellulose, polysaccharidederivatives. Suitable polysaccharide derivatives include: pectine,alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthangum, guar gum. Suitable viscosity modifiers which can be incorporatedinclude synthetic polymeric structurants, e.g., polycarboxylates,polyacrylates, hydrophobically modified ethoxylated urethanes,hydrophobically modified non-ionic polyols; wherein the polycarboxylatepolymer may include one or more of a polyacrylate, and polymethacrylate;a copolymer of unsaturated mono- or di-carbonic acid and C₁-C₃₀ alkylester of the (meth)acrylic acid.

In embodiments, the ionic strength modifiers can include one or morecarboxylic acid, polycarboxylate, phosphate, phosphonate, polyphosphate,polyphosphonate, and borate. In embodiments, the ionic strengthmodifiers can further include one or more ionic species, such as one ormore of oxydisuccinic acid, aconitic acid, citric acid, tartaric acid,malic acid, maleic acid, fumaric acid, succinic acid, sepacic acid,citaconic acid, adipic acid, itaconic acid, dodecanoic acid, acrylicacid homopolymers and copolymers of acrylic acid, maleic acid, calcium,magnesium, iron, manganese, cobalt, copper, and zinc ions.

In embodiments, the aesthetics modifiers can include one or morecolorant, such as dyes or pigments and other aesthetic materials.Non-limiting examples of colorants include Rhodamine, Fluorescein,Phathalocyanine, and alumina. In embodiments, the aesthetics modifierscan include non-limiting examples of particles with different shapes andsizes that can include one or more of epoxy coated metalized aluminiumpolyethylene terephthalate, polyester beads, candelilla beads, silicatesand mixtures thereof.

In embodiments, the density modifiers can include one or more ofglycerol, mannitol, sugar alcohols, inorganic salts, ititanium dioxide;zinc oxides; iron oxides; cobalt oxides; nickel oxides; silver oxides;copper oxides; zirconium oxides; silica; silver; zinc; iron; cobalt;nickel; copper; In embodiments, the water soluble gelling agents caninclude one or more Lecithins, Calcium alginate, Agar, Carrageenan,Processed eucheuma seaweed, Locust bean gum, carob gum, Guar gum,Tragacanth, Acacia gum, gum arabic, Xanthan gum, Karaya gum, Tara gum,Gellan gum, Konjac, Polysorbates, Pectins, Ammonium phosphatides,Sucrose acetate isobutyrate, Glycerol esters of wood resins, Cellulose,Cellulose derivatives and fatty Acids.

In embodiments, the aqueous core can include an enzyme stabilizer. Inembodiments, the enzyme stabilizer can include any conventional enzymestabilizer such as water soluble sources of calcium and/or magnesiumions. In embodiments, the enzyme stabilizer can include one or more of areversible protease inhibitor, such as a boron compound includingborate, 4-formyl phenylboronic acid, phenylboronic acid and derivativesthereof, compounds such as calcium formate, sodium formate and1,2-propane diol, and diethylene glycol.

In embodiments of methods of making capsules having an aqueous core, theoil phase can include a precursor. The precursor can be as definedabove.

In embodiments, the precursor, present in the oil phase, can be presentin an amount of about 1 wt % to about 50 wt % based on the total weightof the aqueous phase (which ultimately forms the core). Other suitableamounts include about 1 wt % to about 15 wt %, about 5 wt % to about 30wt %, about 10 wt % to about 20 wt %, about 15 wt % to about 40 wt %,about 25 wt % to about 45 wt %, or about 15 wt % to about 50 wt %, basedon the total weight of the aqueous phase. For example, the oil phase caninclude, based on the total weight of the aqueous phase, about 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24,26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, or 50 wt %.

In embodiments of method of making capsules having an aqueous core,nanoparticles can be present in one or both of the aqueous phase and theoil phase. In embodiments, the nanoparticles are present only in theaqueous phase. In embodiments, the nanoparticles are present only in theoil phase. In embodiments, the nanoparticles are present in both the oilphase and the aqueous phase.

Any of the nanoparticles described above can be used in the aqueousphase. In embodiments, the nanoparticles can be present in a totalamount, whether in one or both of the aqueous and oil phases, of about0.01 wt % to about 10 wt % based on the total weight of the aqueousphase. Other suitable amounts include about 0.05 wt % to about 5 wt %,about 1 wt % to about 10 wt %, about 5 wt % to about 8 wt %, about 2 wt% to about 7 wt %, or about 0.1 wt % to about 1 wt %. For example, thenanoparticles can be present in an amount based on the total weight ofthe aqueous phase of about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07,0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5,6, 7, 8, 9, or 10 wt %.

In embodiments, the method includes admixing the oil phase and theaqueous phase in a ratio of about 10:1 to about 1:1, about 9:1 to about1:1, about 5:1 to about 1:1, about 3:1 to about 1:1, about 5:1 to about2:1, about 3:1 to about 1.5:1. Other suitable ratios include about 10:1,9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1.5:1 or 1:1.

Curing Conditions

In embodiments, whether making an oil-based core or aqueous core, theemulsion can be cured under conditions to solidify the precursor therebyforming the capsules.

In embodiments, the reaction temperature for curing can be increased inorder to increase the rate at which solidified capsules are obtained.Capsules are considered cured when they no longer collapse.Determination of capsule collapse is detailed below.

In embodiments, during the curing step, hydrolysis of Y moieties (fromformula (I) and/or (II)) occurs, followed by the subsequent condensationof a —OH group with either another —OH group or another moiety of type Y(where the 2 Y are not necessarily the same). The hydrolysed precursormoieties will initially condense with the surface moieties of thenanoparticles (provided they contain such moieties). As the shellformation progresses, the precursor moieties will react with saidpreformed shell.

In embodiments, the emulsion can be cured such that the shell precursorundergoes condensation. In embodiments, the emulsion can be cured suchthat the shell precursor reacts with the nanoparticles to undergocondensation. Shown below are examples of the hydrolysis andcondensation steps described herein for silica based shells:

Hydrolysis: ≡Si—OR+H₂O→≡Si—OH+ROH

Condensation: ≡Si—OH+≡Si—OR→□Si—O—Si≡+ROH

≡Si—OH+≡Si—OH→≡Si—O—Si≡+H₂O.

For example, in embodiments in which a precursor of formula (I) or (II)is used, the following describes the hydrolysis and condensation steps:

Hydrolysis: ≡M-Y+H₂O→≡M-OH+YH

Condensation: ≡M-OH+≡M-Y→≡M-O-M≡+YH

≡M-OH+≡M-OH→≡M-O-M≡+H₂O.

Test Methods Mean Shell Thickness Measurement

The capsule shell, including the first shell component and the secondshell component, when present, is measured in nanometers on 20 benefitagent containing delivery capsules making use of a Focused Ion BeamScanning Electron Microscope (FIB-SEM; FEI Helios Nanolab 650) orequivalent. Samples are prepared by diluting a small volume of theliquid capsule dispersion (20 ull with distilled water (1:10). Thesuspension is then deposited on an ethanol cleaned aluminium stub andtransferred to a carbon coater (Leica EM ACE600 or equivalent). Samplesare left to dry under vacuum in the coater (vacuum level: 10⁻⁵ mbar).Next 25-50 nm of carbon is flash deposited onto the sample to deposit aconductive carbon layer onto the surface. The aluminium stubs are thentransferred to the FIB-SEM to prepare cross-sections of the capsules.Cross-sections are prepared by ion milling with 2.5 nA emission currentat 30 kV accelerating voltage using the cross-section cleaning pattern.Images are acquired at 5.0 kV and 100 pA in immersion mode (dwell timeapprox. 10 μs) with a magnification of approx. 10,000.

Images are acquired of the fractured shell in cross-sectional view from20 benefit delivery capsules selected in a random manner which isunbiased by their size, to create a representative sample of thedistribution of capsules sizes present. The shell thickness of each ofthe 20 capsules is measured using the calibrated microscope software at3 different random locations, by drawing a measurement lineperpendicular to the tangent of the outer surface of the capsule shell.The 60 independent thickness measurements are recorded and used tocalculate the mean thickness.

Coefficient of Variation of Capsule Diameter

Capsule size distribution is determined via single-particle opticalsensing (SPOS), also called optical particle counting (OPC), using theAccuSizer 780 AD instrument or equivalent and the accompanying softwareCW788 version 1.82 (Particle Sizing Systems, Santa Barbara, Calif.,U.S.A.), or equivalent. The instrument is configured with the followingconditions and selections: Flow Rate=1 mL/sec; Lower Size Threshold=0.50μm; Sensor Model Number=LE400-05SE or equivalent; Auto-dilution=On;Collection time=60 sec; Number channels=512; Vessel fluid volume=50 ml;Max coincidence=9200. The measurement is initiated by putting the sensorinto a cold state by flushing with water until background counts areless than 100. A sample of delivery capsules in suspension isintroduced, and its density of capsules adjusted with DI water asnecessary via autodilution to result in capsule counts of at most 9200per mL. During a time period of 60 seconds the suspension is analyzed.The range of size used was from 1 μm to 493.3 μm.

Volume Distribution:

${{CoVv}(\%)} = {\frac{\sigma_{v}}{\mu_{v}}*100}$${\sigma \; v} = {\sum\limits_{i = {1\mspace{14mu} {um}}}^{493.3\mspace{14mu} {um}}\; {\left( {x_{i,v}*\left( {D_{i} - \mu_{v}} \right)^{2}} \right)0.5}}$$\mu_{v} = \frac{\sum\limits_{i = {1\mspace{14mu} {um}}}^{493.3\mspace{14mu} {um}}\; \left( {x_{i,v}*d_{i}} \right)}{\sum\limits_{i = {1\mspace{14mu} {um}}}^{493.3\mspace{14mu} {um}}\; x_{i,v}}$

Where:

CoV_(v)—Coefficient of variation of the volume weighted sizedistribution

σ_(v)—Standard deviation of distribution of volume distribution

μ_(v)—mean of the distribution of volume distribution

d_(i)—diameter in fraction i

x_(i,v)—frequency in fraction i (corresponding to diameter i) of volumedistribution

$x_{i,v} = \frac{x_{i,n}*d_{i}^{3}}{\sum\limits_{i = {1\mspace{14mu} {um}}}^{493.3\mspace{14mu} {um}}\; \left( {x_{i,n}*d_{i}^{3}} \right)}$

Nominal Wall Tension Method

The nominal wall tension, T_(R), is calculated using the followingequation as described in “Liu, M. (2010). Understanding the mechanicalstrength of microcapsules and their adhesion on fabric surfaces.Birmingham, United Kingdom: University of Birmingham (Doctoral thesis)”

$T_{R} = \frac{F_{R}}{\pi \; D_{m}}$

where, F_(R) is rupture force of a single microcapsule and Dm isdiameter of a single capsule before compression. The nominal walltension, T_(R), is interpreted as tension or stretch of wall at rupture.The diameter (D_(m)) and the rupture-force value (F_(R)) (also known asthe bursting-force value) of individual capsules are measured via acomputer-controlled micromanipulation instrument system which possesseslenses and cameras able to image the delivery capsules, and whichpossess a fine, flat-ended probe connected to a force-transducer (suchas the Model 403A available from Aurora Scientific Inc., Canada) orequivalent, as described in: Zhang, Z. et al. (1999) “Mechanicalstrength of single microcapsules determined by a novel micromanipulationtechnique.” J. Microencapsulation, vol. 16, no. 1, pages 117-124, andin: Sun, G. and Zhang, Z. (2001) “Mechanical Properties ofMelamine-Formaldehyde microcapsules.” J.

Microencapsulation, vol. 18, no. 5, pages 593-602, and as available atthe University of Birmingham, Edgbaston, Birmingham, UK.

Nominal wall tension is determined as follows:

-   a) A drop of the delivery capsule suspension is placed onto a glass    microscope slide and dried under ambient conditions for several    minutes to remove the water and achieve a sparse, single layer of    solitary capsules on the dry slide. The concentration of capsules in    the suspension is adjusted as needed to achieve a suitable capsule    density on the slide. More than one slide preparation may be needed.-   b) The slide is then placed on a sample-holding stage of the    micromanipulation instrument. Thirty benefit delivery capsules on    the slide(s) are selected for measurement, such that there are ten    capsules selected within each of three pre-determined size bands.    Each size band refers to the diameter of the capsules as derived    from the Accusizer-generated volume-weighted PSD. The three size    bands of capsules are: the Mean Diameter+/−2 μm; the 5^(th)    Percentile Diameter+/−2 μm; and the 90^(th) Percentile Diameter+/−2    μm. Capsules which appear deflated, leaking or damaged are excluded    from the selection process and are not measured.-   c) For each of the 30 selected capsules, the diameter of the capsule    is measured from the image on the micromanipulator and recorded.    That same capsule is then compressed between two flat surfaces,    namely the flat-ended force probe and the glass microscope slide, at    a speed of 2 μm per second, until the capsule is ruptured. During    the compression step, the probe force is continuously measured and    recorded by the data acquisition system of the micromanipulation    instrument.-   d) The diameter (D_(m)) of each capsule is measured using the    experimental apparatus, or equivalent, and method of Zhang, Z.; Sun,    G: “Mechanical Properties of Melamine-Formaldehyde    microcapsules.” J. Microencapsulation, Vol 18, no. 5, pages 593-602,    2001.-   e) The rupture force (F_(R)) is determined for each selected capsule    from the recorded force probe measurements, as demonstrated in    Zhang, Z. et al. (1999) “Mechanical strength of single microcapsules    determined by a novel micromanipulation technique.” J.    Microencapsulation, vol. 16, no. 1, pages 117-124, and in: Sun, G.    and Zhang, Z. (2001) “Mechanical Properties of Melamine-Formaldehyde    microcapsules.” J. Microencapsulation, vol. 18, no. 5, pages    593-602.-   f) The nominal wall tension (T_(R)) of each of the 30 capsules is    calculated by dividing the rupture force (F_(R)) (in Newtons) by the    diameter of the capsules (D_(m)) multiplied by 7c as described in    “Liu, M. (2010). Understanding the mechanical strength of    microcapsules and their adhesion on fabric surfaces. Birmingham,    United Kingdom: University of Birmingham (Doctoral thesis)”.

Effective Volumetric Core-Shell Ratio Evaluation

The effective volumetric core-shell ratio values were determined asfollows, which relies upon the mean shell thickness as measured by theShell Thickness Test Method. The effective volumetric core-shell ratioof capsules where their mean shell thickness was measured is calculatedby the following equation:

$\frac{Core}{Shell} = \frac{\left( {1 - \frac{2*{Thickness}}{D_{caps}}} \right)^{3}}{\left( {1 - \left( {1 - \frac{2*{Thickness}}{D_{caps}}} \right)^{3}} \right)}$

wherein Thickness is the mean shell thickness of a population ofcapsules measured by FIBSEM and the D_(caps) is the mean volume weighteddiameter of the population of capsules measured by optical particlecounting.

This ratio can be translated to fractional core-shell ratio values bycalculating the core weight percentage using the following equation:

${\% \mspace{14mu} {Core}} = {\left( \frac{\frac{Core}{Shell}}{1 + \frac{Core}{Shell}} \right)*100}$

and shell percentage can be calculated based on the following equation:% Shell=100−% Core.

Degree of Branching Method

The degree of branching of the precursors was determined as follows:Degree of branching is measured using (29Si) Nuclear Magnetic ResonanceSpectroscopy (NMR).

Sample Preparation

Each sample is diluted to a 25% solution using deuterated benzene(Benzene-D6 “100%” (D, 99.96% available from Cambridge IsotopeLaboratories Inc., Tewksbury, Mass., or equivalent). 0.015MChromium(III) acetylacetonate (99.99% purity, available fromSigma-Aldrich, St. Louis, Mo., or equivalent) is added as a paramagneticrelaxation reagent. If glass NMR tubes (Wilmed-LabGlass, Vineland, N.J.or equivalent) are used for analysis, a blank sample must also beprepared by filling an NMR tube with the same type of deuterated solventused to dissolve the samples. The same glass tube must be used toanalyze the blank and the sample.

Sample Analysis

The degree of branching is determined using a Bruker 400 MHz NuclearMagnetic Resonance Spectroscopy (NMR) instrument, or equivalent. Astandard silicon (29Si) method (e.g. from Bruker) is used with defaultparameter settings with a minimum of 1000 scans and a relaxation time of30 seconds.

Sample Processing

The samples are stored and processed using system software appropriatefor NMR spectroscopy such as MestReNova version 12.0.4-22023 (availablefrom Mestrelab Research) or equivalent. Phase adjusting and backgroundcorrection are applied. There is a large, broad, signal present thatstretches from −70 to −136 ppm which is the result of using glass NMRtubes as well as glass present in the probe housing. This signal issuppressed by subtracting the spectra of the blank sample from thespectra of the synthesized sample provided that the same tube and thesame method parameters are used to analyze the blank and the sample. Tofurther account for any slight differences in data collection, tubes,etc., an area outside of the peaks of interest area should be integratedand normalized to a consistent value. For example, integrate −117 to−115 ppm and set the integration value to 4 for all blanks and samples.

The resulting spectra produces a maximum of five main peak areas. Thefirst peak (Q0) corresponds to unreacted TAOS. The second set of peaks(Q1) corresponds to end groups. The next set of peaks (Q2) correspond tolinear groups. The next set of broad peaks (Q3) are semi-dendriticunits. The last set of broad peaks (Q4) are dendritic units. When PAOSand PBOS are analyzed, each group falls within a defined ppm range.Representative ranges are described in the following table:

# of Bridging Oxygen Group ID per Silicon ppm Range Q0 0 −80 to −84 Q1 1−88 to −91 Q2 2 −93 to −98 Q3 3 −100 to −106 Q4 4 −108 to −115

Polymethoxysilane has a different chemical shift for Q0 and Q1, anoverlapping signal for Q2, and an unchanged Q3 and Q4 as noted in thetable below:

# of Bridging Oxygen Group ID per Silicon ppm Range Q0 0 −78 to −80 Q1 1−85 to −88 Q2 2 −91 to −96 Q3 3 −100 to −106 Q4 4 −108 to −115

The ppm ranges indicated in the tables above may not apply to allmonomers. Other monomers may cause altered chemical shifts, however,proper assignment of Q0-Q4 should not be affected.

Using MestReNova, each group of peaks is integrated, and the degree ofbranching can be calculated by the following equation:

${{Degree}\mspace{14mu} {of}\mspace{14mu} {Branching}} = {1\text{/}4\frac{{3^{*}Q\; 3} + {4^{*}Q\; 4}}{{Q\; 1} + {Q\; 2} + {Q\; 3} + {Q\; 4}}}$

Molecular Weight and Polydispersity Index Determination Method

The molecular weight (Polystyrene equivalent Weight Average MolecularWeight (Mw)) and polydispersity index (Mw/Mn) of the condensed layerprecursors described herein are determined using Size ExclusionChromatography with Refractive Index detection. Mn is the number averagemolecular weight.

Sample Preparation

Samples are weighed and then diluted with the solvent used in theinstrument system to a targeted concentration of 10 mg/mL. For example,weigh 50 mg of polyalkoxysilane into a 5 mL volumetric flask, dissolveand dilute to volume with toluene. After the sample has dissolved in thesolvent, it is passed through a 0.45 um nylon filter and loaded into theinstrument autosampler.

Sample Analysis

An HPLC system with autosampler (e.g. Waters 2695 HPLC SeparationModule, Waters Corporation, Milford Mass., or equivalent) connected to arefractive index detector (e.g. Wyatt 2414 refractive index detector,Santa Barbara, Calif., or equivalent) is used for polymer analysis.Separation is performed on three columns, each 7.8 mm I.D.×300 mm inlength, packed with 5 μm polystyrene-divinylbenzene media, connected inseries, which have molecular weight cutoffs of 1, 10, and 60 kDA,respectively. Suitable columns are the TSKGel G1000HHR, G2000HHR, andG3000HHR columns (available from TOSOH Bioscience, King of Prussia, Pa.)or equivalent. A 6 mm I.D.×40 mm long 5 μm polystyrene-divinylbenzeneguard column (e.g. TSKgel Guardcolumn HHR-L, TOSOH Bioscience, orequivalent) is used to protect the analytical columns. Toluene (HPLCgrade or equivalent) is pumped isocratically at 1.0 mL/min, with boththe column and detector maintained at 25° C. 100 μL of the preparedsample is injected for analysis. The sample data is stored and processedusing software with GPC calculation capability (e.g. ASTRA Version6.1.7.17 software, available from Wyatt Technologies, Santa Barbara,Calif. or equivalent.)

The system is calibrated using ten or more narrowly dispersedpolystyrene standards (e.g. Standard ReadyCal Set, (e.g. Sigma Aldrich,PN 76552, or equivalent) that have known molecular weights, ranging fromabout 0.250-70 kDa and using a third order fit for the Mp versesRetention Time Curve.

Using the system software, calculate and report Weight Average MolecularWeight (Mw) and PolyDispersity Index (Mw/Mn).

Benefit Agent Permeability Test

The permeability test method allows the determination of a percentage ofdiffusion of a specific molecule from the capsule core for a populationof capsules into the continuous phase, which can be representative ofthe permeability of the capsule shells. The permeability test method isa referential frame that relates to shell permeability for a specificmolecular tracer, hence fixing its size and its affinity towards thecontinuous phase exterior to the capsule shell. This is a referentialframe that is used to compare the permeability of various capsules inthe art. When both molecular tracer and continuous phase are fixed, theshell permeability is the single capsule property being assessed under aspecific set of conditions.

The capsule shell permeability which correlates with shell porosity,such that low permeability is indicative of low shell porosity.

Capsule permeability is generally given as a function of parameters,such as the shell thickness, concentration of active within the core,solubility of the active in the core, the shell and the continuousphase, etc.

For diffusion of an active to occur across a shell, it must betransferred from the core into the shell, and from the shell into thecontinuous phase. This latter step is rapid if the solubility of theactive in the continuous phase is highly favored, which is the case ofhydrophobic materials into a surfactant-based matrix. For example, anactive that is present at levels of 0.025 w % in a system is very likelyto be fully solubilized into 15 w % of surfactants.

Considering the above, the limiting step to allow for minimal shellpermeability for an active in a surfactant-based matrix, is to limit thediffusion across the shell. For hydrophobic shell materials, ahydrophobic active is readily soluble in the shell in case it can beswollen by said active. This swellability can be limited by high shellcrosslink densities.

For hydrophilic shell materials, such as silicon dioxide, a hydrophobicmaterial has limited solubility in the shell itself. Nevertheless, anactive is capable of rapidly diffusing out when considering thefollowing factors: surfactant molecules and micelles are capable ofdiffusing into the shell, and subsequently into the core itself, whichallows for a pathway from the core into the shell and finally theexterior matrix.

Therefore, in the case of hydrophilic shell materials, a high shellcrosslink density is required, but also reduced quantity of pores withinthe shell. Such pores can lead to fast mass transfer of an active into asurfactant-based matrix. Thus, there is a clear and obvious link betweenthe overall permeability of a capsule shell and its porosity. In fact,the permeability of a capsule gives insight into the overall shellarchitecture of any given capsule.

As discussed previously, diffusion of an active is defined by the natureof the active, its solubility in the continuous phase, and the shellarchitecture (porosity, crosslink density and any general defects itmight contain). Therefore, by fixing two of the three relevantparameters, we can in effect compare the permeability of various shells.

The purpose of this permeability test is to provide such a frameworkthat allows for direct comparisons of different capsule shells.Moreover, it allows for the evaluation of the properties of a largepopulation of capsules and therefore does not suffer from skewed resultsobtained by outliers.

Therefore, the capsule permeability can be defined via the fraction of agiven molecular tracer that diffused into a given continuous phasewithin a given period of time under specific conditions (e.g. 20% tracerdiffusion within 7 days).

Capsules of this invention will have a relative permeability as measuredby the Permeability Test Method of less than about 80%, less than about70%, less than about 60%, less than about 50%, less than about 40%, lessthan about 30%, or less than about 20%.

The Permeability Test Method determines the shell permeability for amolecular tracer, Verdyl Acetate (CAS #5413-60-5) (Vigon) from capsulescontaining the tracer in their core relative to reference samplerepresenting complete diffusion of the said tracer (e.g. 100%permeability).

First, capsules are prepared according to any given capsules preparationmethod. For purposes of the Permeability Test method the capsule coremust include or be supplemented during preparation to include at least10% by weight of the core of the Verdyl Acetate tracer. The “weight ofthe core” in this test refers to the weight of the core after the shellhas been formed and the capsule is made. The capsule core otherwiseincludes its intended components such as core modifiers and benefitagents. Capsules can be prepared as a capsule slurry as is commonly donein the art.

The capsules are then formulated into a Permeability Test sample. ThePermeability Test sample includes mixing enough of the capsule slurrywith an aqueous solution of sodium dodecyl sulfate (CAS #151-21-3) toachieve a total core oil content of 0.25 wt % 0.025% and a SDSconcentration of 15 wt % 1 wt % based on the total weight of the testsample. The amount of capsules slurry needed can be calculated asfollows:

$\frac{{Mass}\mspace{14mu} ({slurry})*{OilActivity}\mspace{14mu} ({slurry})}{{{Mass}\mspace{14mu} \left( {{SDS}\mspace{14mu} {solution}} \right)} + {{Mass}\mspace{14mu} ({Slurry})}} = {0.2500\mspace{14mu} {wt}\mspace{14mu} \%}$

where the OilActivity of the slurry is the wt % of oil in the slurry asdetermined via the mass balance of the capsule making process.

The SDS solution can be prepared by dissolving SDS pellets in deionizedwater. The capsules and the SDS solution can be mixed under conditionsdesigned to prevent breakage of the capsules during mixing. For example,the capsules and the SDS solution can be mixed together by hand or withan overhead mixer, but should not be mixed with a magnetic stir bar. Ithas been found that mixing by magnetic stir bar often leads to breakageof the capsules. Suitable mixtures can include an IKA propeller typemixer, at no more than 400 rpm, wherein the total mass of the mixtureincluding SDS solution and capsule slurry is from 10 g to 50 g. Othersuitable mixing equipment and suitable conditions for mixing without useof magnetic stir bars and without breakage a given capsules compositionwould be readily apparent to the skilled person.

Once prepared, the Permeability Test sample is placed in a glass vialhaving a total volume of no more than two times the volume of thePermeability Test sample and sealed with an airtight lid. The sealedPermeability Test sample is stored at 35° C. and 40% relative humidityfor seven days. During storage, the sealed Permeability Test sample isnot exposed to light and is not opened at any point prior tomeasurement.

A reference sample representing 100% diffusion is also prepared. Thereference sample is prepared to be ready on the day of measurement(i.e., seven days after preparation of the Permeability Test sample.)The reference sample is prepared by combining a free oil mixtureintended to duplicate the composition of the core of the capsules asdetermined by mass balance of the capsule making in the PermeabilityTest sample, including the same percentage by weight of the core of theVerdyl Acetate tracer, with 15% by weight aqueous SDS. The free oilmixture and the SDS solution are homogenized with a magnetic stirreruntil complete solubilization of the free oil mixture, and the vesselshould be sealed during mixing to avoid evaporation of the tracer. Ifthe homogenization takes considerable time, this must be considered andthe starting of the preparation of the reference can be started beforeday 7 if necessary. Immediately after solubilization, the referencesample is placed into a glass vial no more than two times the volume ofthe reference sample and sealed with an airtight lid. The SDS solutioncan be prepared as in the Permeability Test sample by dissolving SDSpellets in deionized water.

The amount of free oil mixture is added to achieve a total concentrationof free oil mixture in the reference sample of 0.25 wt % 0.025% based onthe total weight of the reference sample, as calculated by thefollowing:

$\frac{{Mass}\mspace{14mu} \left( {{Capsule}\mspace{14mu} {core}} \right)}{{{Mass}\mspace{14mu} \left( {{SDS}\mspace{14mu} {solution}} \right)} + {{Mass}\mspace{14mu} \left( {{Capsule}\mspace{14mu} {core}} \right)}} = {0.2500\mspace{14mu} w\mspace{14mu} \%}$

Permeability, as represented by a gas chromatography area count of theVerdyl Acetate, is analyzed for the Permeability Test sample (afterseven days) and the reference sample on the same day using the sameGC/MS analysis equipment. In particular, for each sample, test andreference, aliquots of 100 μL of sample are transferred to 20 mlheadspace vials (Gerstel SPME vial 20 ml, part no. 093640-035-00) andimmediately sealed (sealed with Gerstel Crimp caps for SPME, part no.093640-050-00). Three headspace vials are prepared for each sample. Thesealed headspace vials are then allowed to equilibrate. Samples reachequilibrium after 3 hours at room temperature, but can be left to sitlonger without detriment or change to the results, up until 24 hoursafter sealing the headspace vial. After equilibrating, the samples areanalyzed by GC/MS.

GS/MS analysis are performed by sampling the headspace of each vial viaSPME (50/30 μm DVB/Carboxen/PDMS, Sigma-Aldrich part #57329-U), with avial penetration of 25 millimeters and an extraction time of 1 minute atroom temperature. The SPME fiber is subsequently on-line thermallydesorbed into the GC injector (270° C., splitless mode, 0.75 mm SPMEInlet liner (Restek, art #23434) or equivalent, 300 seconds desorptiontime and injector penetration of 43 millimeters). Verdyl acetate isanalyzed by fast GC/MS in full scan mode. Ion extraction of the specificmass for Verdyl Acetate (m/z=66) is used to calculate the Verdyl Acetate(and isomers) headspace response (expressed in area counts). Theheadspace responses for the Permeability Test sample and the referencesample are referenced herein as Verdyl Acetate Area Count forPermeability Test Sample and Verdyl Acetate Area Count for ReferenceSample, respectively.

Suitable equipment for use in this method includes Agilent 7890B GC with5977MSD or equivalent, Gerstel MPS, SPME (autosampler), GC column:Agilent DB-5UI 30 m×0.25×0.25 column (part #122-5532UI).

Analysis of the Permeability Test sample and the reference sample shouldbe done on the same equipment, under the same room temperatureconditions, and on the same day, each immediately after the other one

Based on the GC/MS data and the actual known content of Verdyl Acetatein the Permeability Test sample, the percent permeability can becalculated. The actual content of Verdyl Acetate in the PermeabilityTest must be determined to correct for any losses during the making ofthe capsules. The method to be used is specified below. This accountsfor inefficiencies often encountered when encapsulating products in acapsule core, and less than the entire anticipated amount of VerdylAcetate present during formation of the capsules being present in theslurry (e.g. evaporation). The following equation can be used tocalculate the percent permeability.

${\frac{{Verdyl}\mspace{14mu} {Acetate}\mspace{14mu} {Area}\mspace{14mu} {Count}\mspace{14mu} {for}\mspace{14mu} {Leakage}\mspace{14mu} {Test}\mspace{14mu} {Sample}}{{Verdyl}\mspace{14mu} {Acetate}\mspace{14mu} {Area}\mspace{14mu} {Count}\mspace{14mu} {for}\mspace{14mu} {Reference}\mspace{14mu} {Sample}}*\frac{100\%}{{wt}\mspace{14mu} \% \mspace{14mu} {Verdyl}\mspace{14mu} {Acetate}\mspace{14mu} {Actual}}*\frac{{oil}\mspace{14mu} \% \mspace{14mu} {Reference}}{{oil}\mspace{14mu} \% \mspace{14mu} {sample}}} = {\% \mspace{14mu} {permeability}}$

This calculated value is the % permeability of the tested capsules after7 days of storage at 40% relative humidity and 35° C.

To evaluate the actual Verdyl Acetate content in the SDS capsulemixture, an aliquot must be retrieved after the specified storage time.For this, the resulting mixture is to be opened on the same day as thefirst samples are measured, thus ensuring that the vial stays sealedduring storage. First, the mixture must be mixed until homogeneous, sothat a representative aliquot containing the right proportions ofmaterials is retrieved. Then, 1 gram of said homogeneous mixture isintroduced into a flat bottom glass vial of a diameter of 1 cm, and amagnetic stirring bar of a length of no less than half the diameter ofthe vial is introduced into said vial. The homogeneous mixture in thespecified jar containing the magnetic stirbar is sealed and then placedonto a magnetic stirring plate, and a mixing of 500 rpm is used so thatthe stirring action of the stirbar grinds all capsules. This results intotal release of the encapsulated core material into the surrounding SDSsolution, thus allowing for the measurement of the actual VerdylAcetatecontent. The measurement protocol of this content must be performed asfor the unbroken capsules. In addition, prior to the measurement step,the capsules must be observed under an optical microscope to assesswhether all capsules have been broken. If this is not the case, thecapsule grinding must be repeated, with either increasing the mixingspeed and/or the mixing time.

Method of Calculating Organic Content in First Shell Component

Definition of organic moiety in inorganic shell—Any moiety X that cannotbe cleaved from a metal precursor bearing a metal M (where M belongs tothe group of metals and semi-metals, and X belongs to the group ofnon-metals) via hydrolysis of the M-X bond linking said moiety to theinorganic precursor of metal or semi-metal M and under specific reactionconditions, will be considered as organic. A minimal degree ofhydrolysis of 1% when exposed to neutral pH distilled water for aduration of 24 h without stirring, is set as the reaction conditions.

This method allows one to calculate a theoretical organic contentassuming full conversion of all hydrolysable groups. As such, it allowsone to assess a theoretical percentage of organic for any mixture ofsilanes and the result is only indicative of this precursor mixtureitself, not the actual organic content in the first shell component.Therefore, when a certain percentage of organic content for the firstshell component is disclosed anywhere in this document, it is to beunderstood as containing any mixture of unhydrolyzed or pre-polymerizedprecursors that according to the below calculations give a theoreticalorganic content below the disclosed number.

Example for Silane (but not Limited to Silane, See Generic Formulas atthe End of the Document):

Consider a mixture of silanes, with a molar fraction Y for each, andwhere i is an ID number for each silane. Said mixture can be representedas follows:

Si(XR)_(4-n)R_(n)

Where XR is a hydrolysable group under conditions mentioned in thedefinition above, R^(i) _(ni) is non-hydrolyzable under conditionsmentioned above and n; =0, 1, 2 or 3.

Such a mixture of silanes will lead to a shell with the followinggeneral formula:

${SiO}_{\frac{({4 - n})}{2}}R_{n}$

Then, the weight percentage of organic moieties as defined earlier canbe calculated as follows:

1) Find out Molar fraction of each precursor (nanoparticles included)2) Determine general formula for each precursor (nanoparticles included)3) Calculate general formula of precursor and nanoparticle mixture basedon molar fractions4) Transform into reacted silane (all hydrolysable groups to oxygengroups)5) Calculate weight ratio of organic moieties vs. total mass (assuming 1mole of Si for framework)

Example

Raw Mw weight amount Molar material Formula (g/mol) (g) (mmol) fractionSample AY SiO(OEt)₂ 134 1 7.46 0.57 TEOS Si(OEt)₄ 208 0.2 0.96 0.07DEDMS Si(OEt)₂Me₂ 148.27 0.2 1.35 0.10 SiO2 NP SiO₂ 60 0.2 3.33 0.25

To calculate the general formula for the mixture, each atoms index inthe individual formulas is to be multiplied by their respective molarfractions. Then, for the mixture, a sum of the fractionated indexes isto be taken when similar ones occur (typically for ethoxy groups).

Note: Sum of all Si fractions will always add to 1 in the mixturegeneral formula, by virtue of the calculation method (sum of all molarfractions for Si yields 1).

SiO_(1*0.57+2*0.25)(OEt)_(2*0.57+4*0.07+2*0.10)Me_(2*0.10)SiO_(1.07)(OEt)_(1.62)Me_(0.20)

To transform the unreacted formula to a reacted one, simply dividing theindex of ALL hydrolysable groups by 2, and then adding them together(with any pre-existing oxygen groups if applicable) to obtain the fullyreacted silane

SiO_(1.88)Me_(0.20)

In this case, the expected result is SiO_(1.9)Me_(0.2), as the sum ofall indexes must follow the following formula:

A+B/2=2,

where A is the oxygen atom index and B is the sum of allnon-hydrolysable indexes. The small error occurs from rounding up duringcalculations and should be corrected. The index on the oxygen atom isthen readjusted to satisfy this formula.

Therefore, the final formula is SiO_(1.9)Me_(0.2), and the weight ratioof organic is calculated below:

Weight ratio: =(0.20*15)/(28+1.9*16+0.20*15)=4.9%

General Case:

The above formulas can be generalized by considering the valency of themetal or semi-metal M, thus giving the following modified formulas:

M(XR)_(V-m)R^(i) _(m)

And using a similar method but considering the valency V for therespective metal.

EXAMPLES

While particular embodiments of the present disclosure have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the disclosure. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this disclosure.

Example 1: Non-Hydrolytic Precursor Synthesis

The Precursors for Samples A-S, AV-AAD were made by the followingmethod:

A quantity of TAOS reagent(s) (available from Sigma Aldrich) were addedto a clean dry round bottom flask equipped with a stir bar anddistillation apparatus under nitrogen atmosphere. A volume of aceticanhydride (available from Sigma Aldrich) and catalyst (available fromGelest, Sigma Aldrich) were added and the contents of the flask werestirred and heated as indicated in the Table 1. The reaction was heatedto the indicated temperature for the indicated amount of time, duringwhich the organic ester generated by reaction of the alkoxy silanegroups with acetic anhydride was distilled off along with additionalorganic esters generated by the condensation of silyl-acetate groupswith other alkoxysilane groups which occurred as the polyalkoxysilane(PAOS) was generated. The reaction flask was cooled to room temperatureand placed on a rotary evaporator (Buchi Rotovapor R110), used inconjunction with a water bath and vacuum pump (Welch 1402 DuoSeal) toremove any remaining solvent. All reactant and reagent types and ratios,catalysts and ratios, and all reaction conditions (e.g. time andtemperature) are detailed in Table 1.

The following reactants can be abbreviated as follows: tetraethoxysilane(TEOS), tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS),triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS),trimethylethoxysilane (TMES), tetraacetoxysilane (TAcS), and titaniumtetrabutoxide (TTB).

Example 2: Hydrolytic Precursor Synthesis

The Precursors for Samples U-Z, AA-AI, and AK-AAB were made by thefollowing method:

A quantity of TAOS reagent(s) (available from Sigma Aldrich) was addedto a clean dry round bottom flask equipped with a stir bar anddistillation apparatus under nitrogen atmosphere and to which was addeda quantity of alcohol (available from Sigma Aldrich). A quantity ofcatalyst dissolved in water was added as indicated in the Table 2. 1Nand 0.1N HCl dissolved in water are available from Sigma Aldrich. 0.002NHCl was prepared by diluting 0.1N HCl in distilled water (available fromSigma Aldrich). The reaction was stirred and heated to the indicatedtemperature for the indicated amount of time during which the alcoholgenerated by hydrolysis of the alkoxy silane groups and the alcoholsolvent were both distilled off along with some of the water generatedby the condensation of silanol groups which occurred as thepolyalkoxysilane (PAOS) is generated. The reaction flask is cooled toroom temperature and placed on a rotary evaporator (Buchi RotovaporR110), used in conjunction with a water bath and vacuum pump (Welch 1402DuoSeal) to remove any remaining solvent. All reactant and reagent typesand ratios, catalysts and ratios, and all reaction conditions (e.g. timeand temperature) are detailed in Table 2.

In some samples, such as Samples AB and AC, further reaction was needed,identified as Step 2 in Table 2 below. In Step 2, the procedure asdescribed above was repeated except with the product from the abovedescribed reaction as the starting material. All reactant and reagenttypes and ratios, catalysts and ratios, and all reaction conditions(e.g. time and temperature) are detailed in Table 2.

TABLE 1 Non-Hydrolytic Synthesis Mole TAOS Mole Ratio Ratio Precursoramount Reagent/ Catalyst/ ID and ID Reagent TAOS Catalyst TAOS A 50 gTMOS Acetic 1 Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride B 50 gTEOS Acetic 1 Titanium Ethoxide 0.3% Anhydride C 50 g TEOS Acetic 0.8Titanium Butoxide 0.3% Anhydride D 50 g TEOS Acetic 1 Titanium Butoxide0.3% Anhydride E 50 g TEOS Acetic 1 Titanium Butoxide 0.15%  Anhydride F50 g TEOS Acetic 1.2 Titanium Butoxide 0.3% Anhydride G 50 g TEOS Acetic0.7 Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride H 50 g TEOS Acetic0.8 Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride I 50 g TEOS Acetic0.9 Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride J 50 g TEOS Acetic1 Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride K 50 g TEOS Acetic1.2 Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride L 50 g TEOS/ Acetic1:1:2 Tetrakis(trimethylsiloxy)titanium 0.3% 37.2 g Anhydride(TEOS:TMOS:AA) TMOS M 50 g TBOS Acetic 1Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride N 50 g TBOS Acetic 1.2Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride O 50 g TEOS/ Acetic 1Tetrakis(trimethylsiloxy)titanium 0.3% 5 g TEMS Anhydride P 50 g TEOS/Acetic 1 Tetrakis(trimethylsiloxy)titanium 0.3% 5 g Anhydride DEDMS R 50g TEOS/ Acetic 1 Tetrakis(trimethylsiloxy)titanium 0.3% 2 g TMESAnhydride S 50 g Acetic 1 None n/a TEOS/ Anhydride 10 g TTB AV 50 gTEOS/ Acetic 1 None n/a 20 g TTB Anhydride AWchange 75 g TEOS Acetic 1Tetrakis(trimethylsiloxy)titanium 0.3% Anhydride AX 1,000 g Acetic 1Tetrakis(trimethylsiloxy)titanium 0.3% TEOS Anhydride AY 200 g Acetic 1Tetrakis(trimethylsiloxy)titanium 0.3% TEOS Anhydride AZ 350 g Acetic1.1 Tetrakis(trimethylsiloxy)titanium 0.3% TEOS Anhydride AAA 750 gAcetic 1 Tetrakis(trimethylsiloxy)titanium 0.3% TEOS Anhydride AAC 150 gAcetic 1.2 Titanium Tetraethoxide 0.3% TEOS Anhydride AAD 200 g Acetic1.2 Tetrakis(trimethylsiloxy)titanium 0.3% TEOS Anhydride PrecursorTemp. Physical Degree of ID Profile Appearance Branching Mw*** PDI A 50°C. for Sand n/a* n/a* n/a* 1 hour then ramp to 100° C. for 1 hour B 135°C. Liquid 0.18 1 1.7 for 8 hours C 135° C. Liquid 0.22 1.6 1.7 for 8hours D 135° C. Viscous 0.27 3.3 2.9 for 8 Liquid hours E 135° C.Viscous 0.26 3.9 3.7 for 8 Liquid hours F 135° C. Viscous 0.30 7.2 4.6for 8 Liquid hours G 135° C. Liquid 0.14 0.5 2.2 for 8 hours H 135° C.Liquid 0.10 1.1 1.2 for 8 hours I 135° C. Liquid 0.20 0.9 2.5 for 8hours J 135° C. Viscous 0.26 2.3**   2.1** for 24 Liquid hours K 135° C.Viscous 0.39 3.7 5.6 for 24 Liquid hours L 70° C. for Soft Gel n/a* n/a*n/a* 1 hour Balls then ramp to 120° C. for 2 hours M 130° C. Viscous0.31 1.7 1.3 for 1 hour Liquid then ramp to 180° C. for 24 hours N 130°C. Viscous 0.47 2.5 1.4 for 1 hour Liquid then ramp to 180° C. for 24hours O 135° C. Liquid 0.20 0.9 3.1 for 24 hours P 135° C. Viscous 0.261.2 3.1 for 24 Liquid hours R 135° C. Viscous 0.26 1.3 3.0 for 24 Liquidhours S 135° C. Viscous 0.24 0.9 3.2 for 24 Liquid hours AV 135° C.Viscous 0.27 1.4 2.4 for 24 Liquid hours AWchange 135° C. for Viscous0.25 1.8 2.0 7 hours Liquid AX 135° C. for Viscous 0.26 1.2 3.9 28 hoursLiquid AY 135° C. for Viscous 0.25 1.3 3.9 24 hours Liquid AZ 135° C.for Viscous 0.29 1.5 4.9 30 hours Liquid AAA 135° C. for Viscous 0.261.4 1.8 24 hours Liquid AAC 135° C. for Viscous 0.36 3.8 7.4 24 hoursLiquid AAD 135° C. for Viscous 0.43 10 6.6 60 hours Liquid *Samples pastgel point. Characterization data not available, **Results are an averageof three synthesized materials *** Polystyrene equivalent Weight AverageMolecular Weight calculated as described above

TABLE 2 Hydrolytic Synthesis Additional Mole Ratio Moles Pre- TAOSReagent/ Solvent Step 2 Reagent/ Temp. Physical cursor amount Reagent/Catalyst/ Amount Temp. Reagent/ Catalyst Profile Appear- Degree of MW IDand ID Catalyst TAOS and ID Profile Catalyst Added Solvent Step 2 anceBranching (kDa) PDI U 50 g H₂O/0.1N 0.5/ 65 mL 70° C. for 1 — — — —Liquid 0.07 < — TMOS HCl 0.00216/1 MeOH hour then LOD ramp to 115° C.for 7 hours V 50 g H₂O/0.1N 1/ 65 mL 70° C. for 1 — — — — Liquid 0.210.1 4.4 TMOS HCl 0.00433/1 MeOH hour, ramp 115° C. for 7 hrs, thenreduce back to 70° C. for 16 hours W 50 g H₂O/0.1N 1.25/ 65 mL 70° C.for 1 — — — — Viscous 0.30 3.3 1.3 TMOS HCl 0.00541/1 MeOH hour thenLiquid ramp to 115° C. for 7 hours X 50 g H₂O/0.1N 1.5/ 65 mL 70° C. for1 — — — — Gel n/a* n/a* n/a* TMOS HCl 0.00650/1 MeOH hour then ramp to115° C. for 7 hours Y 50 g H₂O/0.1N 0.61/ 60 mL 80° C. for 1 — — — —Liquid 0.20 1.4 1.3 TEOS HCl 0.00264/1 EtOH hour, ramp 120° C. for 7,then reduce back to 80° C. for 60 hours Z 50 g H₂O/0.1N 1/ 60 mL 80° C.for 1 — — — — Liquid 0.11 0.6 1.2 TEOS HCl 0.00433/1 EtOH hour then rampto 120° C. for 24 hours AA 50 g H₂O/1.0N 0.61/ 60 mL 80° C. for 1 — — —— Liquid 0.14 0.7 1.1 TEOS HCl 0.0264/1 EtOH hour then ramp to 120° C.for 7 hours AB 50 g H₂O/1.0N 0.5/ 60 mL 80° C. for 1 H₂O/ 0.11/0.0835 60mL 80° C. Liquid 0.21 < — TEOS HCl 0.0287/1 EtOH hour then 1.0N EtOH for1 LOD ramp to HCl hour 120° C. for then 7 hours ramp to 120° C. for 7hours AC 50 g H₂O/ 0.5/ 60 mL 80° C. for 1 H₂O/ 0.11/9.5^(E−6) 60 mL 80°C. Viscous 0.25 3.7 2.8 TEOS 0.002N 4.33^(E−5)/1 EtOH hour then 0.002NEtOH for 1 Liquid HCl ramp to HCl hour 120° C. for then 7 hours ramp to120° C. for 7 hours AD 50 g H₂O/Acetic 1/1/1 50 mL 80° C. for 1 — — — —Viscous 0.32 3.5 1.7 TEOS Acid EtOH hour then Liquid ramp to 120° C. for24 hours AE 50 g H₂O/Acetic 1.5/1.5/1 50 mL 80° C. for 1 — — — — Sandn/a* n/a* n/a* TEOS Acid EtOH hour then ramp to 120° C. for 24 hours AF50 g H₂O/0.1N 1/ 60 mL 65° C. for 1 — — — — Liquid 0.13 0.4 1.6 TEOS/HCl 0.00433/1 MeOH hour then ramp to 100° C. for 7 hours AG 50 g H₂O1/0/1 62 mL 80° C. for 1 — — — — Viscous 0.27 0.6 1.3 TEOS/ EtOH hourthen Liquid 50g ramp to STC 120° C. for 24 hours AH 50 g H₂O/0.1N 1/ 56mL 80° C. for 1 — — — — Liquid 0.20 0.6 1.4 TEOS/ HCl 0.00433/1 EtOHhour then 0.5 g ramp to TEMS 120° C. for 24 hours AI 50 g H₂O/0.1N 1/ 62mL 80° C. for 1 — — — — Liquid 0.11 0.7 1.4 TEOS/ HCl 0.00433/1 EtOHhour then 5 g ramp to TEMS 120° C. for 24 hours AK 50 g H₂O/0.1N 0.8/ 45mL 80° C. for 1 — — — — Liquid 0.11 0.7 1.2 TBOS HCl 0.00433/1 EtOH hourthen ramp to 180° C. for 65 hours AL 50 g H₂O/0.1N 1/ 45 mL 80° C. for 1— — — — Liquid 0.15 0.9 1.4 TBOS HCl 0.00433/1 EtOH hour then ramp to180° C. for 65 hours AM 50 g Formic 1.2/0/1 n/a 80° C. for 1 — — — —Viscous 0.27 0.9 7.1 TEOS Acid hour then Liquid ramp to 120° C. for 24hours AN 50 g H₂O/ 1/1/1 70 mL 80° C. for 1 — — — — Gelled n/a* n/a*n/a* TEOS Formic EtOH hour then Acid ramp to 120° C. for 6 hours AO 50 gH₂O/ 1/0.5/1 70 mL 80° C. for 1 — — — — Liquid 0.15 0.9 2.9 TEOSTrifluoro EtOH hour then Acetic ramp to Acid 120° C. for 24 hours AP 45g H₂O 1/ 62 mL 80° C. for 1 — — — — Viscous 0.21 0.9 1.6 TEOS/ 0.00433/1EtOH hour then Liquid 5 g ramp to TAcS 120° C. for 24 hours AQ 45 gH₂O/0.1N 1/ 56 mL 80° C. for 1 — — — — Liquid 0.11 0.5 1.3 TEOS/ HCl0.00433/1 EtOH hour then 5 g ramp to TEMS 120° C. for 24 hours AR 45 gH₂O/0.1N 1/ 58 mL 80° C. for 1 — — — — Liquid 0.10 0.5 1.3 TEOS/ HCl0.00433/1 EtOH hour then 5 g ramp to DEDMS 120° C. for 24 hours AS 48 gH₂O/0.1N 1/ 55 mL 80° C. for 1 — — — — Liquid 0.10 0.6 1.4 TEOS/ HCl0.00433/1 EtOH hour then 2 g ramp to TMES 120° C. for 24 hours AT 90 gH₂O/0.1N 1/ 114 mL 80° C. for 1 — — — — Viscous 0.23 0.8 1.5 TEOS/ HCl0.00433/1 EtOH hour then Liquid 8 g ramp to TEMS/ 120° C. for 2 g 24hours TMES AU 50 g H₂O/0.1N 1/ 60 mL 80° C. for 1 — — — — Viscous 0.261.1 3.1 TEOS/ HCl 0.00433/1 EtOH hour then Liquid 10 g ramp to TTB 120°C. for 24 hours AAB 20 g Glacial 2/0/1 0 mL 80° C. for 1 — — — — Liquid0.16 0.6 2.3 TEOS Acetic hour then Acid ramp to 120° C. for Viscous 24hours *Samples past gel point. Characterization data not available

Example 3: Oil-in-Water Capsules

Capsules of Table 3, section A (Samples C, E, F, G, H, I, J, K, L, Q, S,T, Z, AA, AB, AC and comparative example W) were made by the followingmethod:

The oil phase was prepared by mixing and homogenizing (or evendissolving if all compounds are miscible) a precursor with a benefitagent and/or a core modifier. The water phase was prepared by addingacids or bases to water to yield a desired starting pH. Next,nanoparticles were added to the water phase and dispersed with anultrasound bath for at least 30 minutes.

Once each phase was prepared separately, they were combined, and the oilphase was dispersed into the water phase with proper mixing tools, timesand energy to reach a desired mean capsule diameter of the capsules. Ifnot specified otherwise, once the emulsification step was complete, theresulting emulsion was left resting without stirring at a specifictemperature until enough curing had occurred for the capsules to notcollapse. Optionally, in order to deposit a second shell component, thecapsules could receive a post-treatment with a second shell componentsolution, with materials and quantities described in Table 3.

To test whether capsules collapse, the slurry must be at least 10 timesdiluted into de-ionized water. Drops of the subsequent dilution wereadded onto a microscopy microslide and left to dry overnight at roomtemperature. The following day the dried capsules were observed under anoptical microscope by light transmission to assess if the capsules haveretained their spherical shape (without the use of a cover slide)

All reagent types and ratios, and all reaction conditions (e.g. mixing,curing time and temperature) are detailed in Table 3 and the results aredetailed in Table 4. All results were tested or measured in accordancewith the test methods set forth herein.

FIG. 2A illustrates a capsule of Sample Q and FIG. 2B illustrates acapsule shell of Sample Q, of Table 3 and 4. FIG. 3A illustrates anunbroken capsule of Sample I and FIG. 3B illustrates a capsule shell ofSample I, of Table 3 and 4. FIG. 4A illustrates capsules of Sample E andFIG. 4B illustrates a capsule shell of Sample E, of Table 3 and 4. FIG.5 illustrates capsules of Sample C of Table 3 and 4. FIG. 6 illustratesa capsule shell of Sample Z of Table 3 and 4. FIGS. 7A-B illustratecapsules having a substantially inorganic shell comprising a first shellcomponent and a second shell component of Sample G of Table 3 and 4.FIG. 8A illustrates capsules having a substantially inorganic shellcomprising a first shell component and a second shell component ofSample H and FIG. 8B illustrates a capsule shell having a substantiallyinorganic shell comprising a first shell component and a second shellcomponent of Sample H, of Table 3 and 4 and FIG. 9 illustratescollapsing capsule shells of Sample W, of Table 3 and 4. FIG. 10illustrates an energy dispersive X-ray spectrum of a capsule of Sample Kand FIG. 11 illustrates an energy dispersive X-ray spectrum of a capsuleof Sample AA of Tables 3 and 4.

Example 4: Water-in-Oil Capsules

Capsules of Table 3, Section A (Examples N and AD) were made by thefollowing method:

The water phase was prepared by mixing and homogenizing any combinationof the following and at least a benefit agent: water, core modifier,benefit agent and nanoparticles. The oil phase consisted of a largeexcess of a hydrophobic liquid as the continuous phase. The oil phasecan be a solvent or any liquid organic molecule that is substantiallyimmiscible with water. The oil phase included the nanoparticles, whichwere well dispersed into the above hydrophobic liquid for at least 30minutes in an ultrasound bath. The continuous oil phase included themetal oxide precursor prior to or after emulsification, as well as anorganic acid prior to or after emulsification.

Once each phase was prepared separately, they were combined, and thewater phase was dispersed into the oil phase with proper mixing tools,times and energy to reach a desired mean diameter of the capsules. Ifnot specified otherwise, once the emulsification step was complete, theresulting emulsion was left resting without stirring at a specifictemperature until enough curing has occurred for the capsules to notcollapse. Optionally, in order to deposit a second shell component, thecapsules could receive a post-treatment with a second shell componentsolution, with materials and quantities described in Table 3.

To test whether capsules collapse, the slurry must be at least 10 timesdiluted into de-ionized water. Drops of the subsequent dilution wereadded onto a microscopy microslide and left to dry overnight at roomtemperature. The following day the dried capsules were observed under anoptical microscope by light transmission to assess if the capsules haveretained their spherical shape (without the use of a cover slide).

All reagent types and ratios, and all reaction conditions (e.g. mixing,curing time and temperature) are detailed in Table 3 and the results aredetailed in Table 4. All results were tested or measured in accordancewith the test methods set forth herein.

FIGS. 12A and B illustrate capsules of Sample N, of Table 3 and 4.

Example 5: Oil-in-Water Capsules with Variable Shell Organic Percentage

Capsule of Table 3 section B (Examples AF, AH, AJ and comparativeexamples AE, AG, AK, AL, AI, AM, AN, AO, AP) were made by the followingmethod:

The oil phase was prepared by mixing and homogenizing (or evendissolving if all compounds are miscible) a precursor with a benefitagent and/or a core modifier. The water phase was prepared by addingacids or bases to water to yield a desired starting pH. Next,nanoparticles were added to the water phase and dispersed with anultrasound bath for at least 30 minutes.

Once each phase was prepared separately, they were combined, and the oilphase was dispersed into the water phase with proper mixing tools, timesand energy to reach a desired mean capsule diameter of the capsules. Ifnot specified otherwise, once the emulsification step was complete, theresulting emulsion was left resting without stirring at a specifictemperature until enough curing had occurred for the capsules to notcollapse. Optionally, in order to deposit a second shell component, thecapsules could receive a post-treatment with a second shell componentsolution, with materials and quantities described in Table 3.

To test whether the capsules collapse, the slurry must be at least 10times diluted into de-ionized water. Drops of the subsequent dilutionwere added onto a microscopy microslide and left to dry overnight atroom temperature. The following day the dried capsules were observedunder an optical microscope by light transmission to assess if thecapsules have retained their spherical shape (without the use of a coverslide)

All reagent types and ratios, and all reaction conditions (e.g. mixing,curing time and temperature) are detailed in Table 3 and the results aredetailed in Table 4. All results were tested or measured in accordancewith the test methods set forth herein.

Section B of Tables 3 and 4 (making of capsules and resultsrespectively) shows that capsules with an increasing percentage oforganic content in the first shell component have increasedpermeabilities after addition of a second shell component as illustratedby FIG. 13. With first shell components only, the permeability is high,but the capsule can resist air drying without collapsing.

Example 6: Oil-in-Water Capsules with Variable Core/Shell Ratio Values

Capsule of Table 3 section C (Examples AU, AV and comparative examplesB, AQ, AR, AS, AT, AW) were made by the following method:

The oil phase was prepared by mixing and homogenizing (or evendissolving if all compounds are miscible) a precursor with a benefitagent and/or a core modifier. The water phase was prepared by addingacids or bases to water to yield a desired starting pH. Next,nanoparticles were added to the water phase and dispersed with anultrasound bath for at least 30 minutes.

Once each phase was prepared separately, they were combined, and the oilphase was dispersed into the water phase with proper mixing tools, timesand energy to reach a desired mean capsule diameter of the capsules. Ifnot specified otherwise, once the emulsification step was complete, theresulting emulsion was left resting without stirring at a specifictemperature until enough curing had occurred for the capsules to notcollapse. Optionally, in order to deposit a second shell component, thecapsules could receive a post-treatment with a second shell componentsolution, with materials and quantities described in Table 3.

To test whether capsules collapse, the slurry must be at least 10 timesdiluted into de-ionized water. Drops of the subsequent dilution wereadded onto a microscopy microslide and left to dry overnight at roomtemperature. The following day the dried capsules were observed under anoptical microscope by light transmission to assess if the capsules haveretained their spherical shape (without the use of a cover slide)

All reagent types and ratios, and all reaction conditions (e.g. mixing,curing time and temperature) are detailed in Table 3 and the results aredetailed in Table 4. All results were tested or measured in accordancewith the test methods set forth herein.

Examples from Table 3 section C demonstrate the importance of combiningan optimal mean volume weighed capsule diameter (10 um-200 um), meanshell thickness (170 nm-1000 nm) and core shell ratio (80:20-98:2) asdisclosed in this invention, in order to obtain low shell permeabilitiesin accordance with the shell permeability method. FIG. 14 illustratesthe region of interest when plotting examples (permeability <40%) andcomparative examples (permeability >40%). FIG. 15A illustrates a capsuleshell of Sample B (comparative example) with a core shell ratio of 78:22and FIG. 15B illustrates capsules of Sample B, of Table 3 and 4, FIG. 16illustrates a capsule shell of Sample AW (comparative example) of Table3 and 4 with a core:shell ratio of 99:1.

Example 7: Oil-in-Water Capsules Prepared with Variable First ShellComponent Precursor Degree of Branching and Molecular Weight

Capsule of Table 3 section D (Examples AAA, AAB, AAC and comparativeexamples AX, AY, AAD, AAE, AAF) were made by the following method:

The oil phase was prepared by mixing and homogenizing (or evendissolving if all compounds are miscible) a precursor with a benefitagent and/or a core modifier. The water phase was prepared by addingacids or bases to water to yield a desired starting pH. Next,nanoparticles were added to the water phase and dispersed with anultrasound bath for at least 30 minutes.

Once each phase was prepared separately, they were combined, and the oilphase was dispersed into the water phase with proper mixing tools, timesand energy to reach a desired mean capsule diameter of the capsules. Ifnot specified otherwise, once the emulsification step was complete, theresulting emulsion was left resting without stirring at a specifictemperature until enough curing had occurred for the capsules to notcollapse. Optionally, in order to deposit a second shell component, thecapsules could receive a post-treatment with a second shell componentsolution, with materials and quantities described in Table 3.

To test whether capsules collapse, the slurry must be at least 10 timesdiluted into de-ionized water. Drops of the subsequent dilution wereadded onto a microscopy microslide and left to dry overnight at roomtemperature. The following day the dried capsules were observed under anoptical microscope by light transmission to assess if the capsules haveretained their spherical shape (without the use of a cover slide)

All reagent types and ratios, and all reaction conditions (e.g. mixing,curing time and temperature) are detailed in Table 3 and the results aredetailed in Table 4. All results were tested or measured in accordancewith the test methods set forth herein.

Capsule data in the Table 3 section D shows that capsules made with PAOShaving a Degree of Branching below 0.2 and a Molecular weight below 700Da present a shell permeability higher than 40% and/or do not resist airdrying without collapsing as represented by the graph in FIG. 17.

By way of example, the following is a detailed description of theapplication of the Permeability Test Method to determine the shellpermeability of capsules of example R from Tables 3 and 4 below.

Verdyl acetate was present at a level of 13 w % in the fragrancecomposition.

Capsule slurry obtained in example R from Table 3 had an oil activity of19.04% based on the mass balance of the capsule making protocol. 0.131 gof this slurry was weighed into 9.87 g of a 15 w % SDS (aq.) solution toyield a product with an oil concentration of 0.249 w % and an SDSconcentration of 14.53%. The resulting mixture was well dispersed bygently shaking the vial by hand in a circular motion. The glass vial washermetically sealed with an airtight lid and stored at 35 degreesCelsius and 40% humidity for 7 days. The day of product making isconsidered as day 0. It was found that the actual Verdyl Acetate contentin the sample was corresponding to the theoretical value.

On day 7, the reference sample was prepared by weighing 0.126 g of theoil used for the capsule making into 49.88 g of a 15 w % SDS (aq.)solution to yield a reference sample with an oil concentration of 0.252%and an SDS concentration of 14.96%. The resulting mixture was stirredwith the aid of a magnetic stirrer in a sealed jar until completesolubilization of the oil. The reference sample was kept aside andstored at room temperature.

Prior to measurement, the product containing capsules was removed fromstorage. The capsules had settled to the bottom of the vial. Thecapsules were re-dispersed by gently shaking the vial in a circularmotion, until the whole volume of liquid was turbid. Immediately aftercapsule re-dispersion, using a positive displacement pipette (fromEppendorf), 100 microL aliquots were inserted into the bottom of 3separate headspace vials, and immediately sealed with a crimp cap.

The same operation was performed for the reference product.

After 3 hours of equilibration at room temperature, the first replicateof reference product containing vial was measured via headspace GC/MS asoutlined in the test methods section. Once the GC oven had cooled downto the starting temperature, the next replicate was immediatelymeasured, and so on until all replicates of references and capsulescontaining products have been analyzed.

The ion chromatogram for M/Z of 66 was extracted, the peakscorresponding to Verdyl acetate and its isomers were identified byreading the full mass spectra and comparing to literature. Theseidentified peaks were then integrated to yield an Area under the peaks.An average of the areas of the 3 replicates was made for the referenceand capsule samples respectively (Table A below):

TABLE A ID AREA UNDER PEAK REFERENCE_1 71714 REFERENCE_2 74537REFERENCE_3 73447 CAPSULE_1 49225 CAPSULE_2 46713 CAPSULE_3 53256

Average Area for reference was 73233 and the average Area for thecapsule containing product was 49731, based on the table above.

${\frac{{Verdyl}\mspace{14mu} {Acetate}\mspace{14mu} {Area}\mspace{14mu} {Count}\mspace{14mu} {for}\mspace{14mu} {sample}\mspace{14mu} {containing}\mspace{14mu} {capsules}}{{Verdyl}\mspace{14mu} {Acetate}\mspace{14mu} {Area}\mspace{14mu} {Count}\mspace{14mu} {for}\mspace{14mu} {Reference}\mspace{14mu} {Sample}}*\frac{100\%}{\% \mspace{14mu} {Actual}\mspace{14mu} {VBerdyl}\mspace{14mu} {Acetate}\mspace{14mu} {{vs}.\mspace{14mu} {theoretical}}\mspace{14mu} {Verdyl}\mspace{14mu} {Acetate}}*\frac{{oil}\mspace{14mu} \% \mspace{14mu} {reference}}{{oil}\mspace{14mu} \% \mspace{14mu} {sample}}} = {{\frac{49731}{73233}*\frac{100\%}{100\%}*\frac{0.252\%}{0.249\%}} = {68.7\%}}$

shell permeability for Verdyl acetate after 7 days of storage at 35degrees Celsius and 40% relative humidity.

TABLE 3 Examples capsule preparation Section A Capsule making Sam-Precursor Curing Second shell component ple (Tables temp. solutionmaterial and ID Emulsion Oil phase 1-4) Water phase Emulsification (°C.) quantity F Oil in 1.2 g fragrance oil and K 8 g of a 1.75w% Aerosil300 5 min. at 8000rpm d 1 g of 10w% of Sodium water 0.8 g precursordispersion in 0.1M HCl (IKA ultraturrax silicate(aq.) solution.S25N-10G) Conditions e G Oil in 1.6 g fragrance oil and J 8 g of a 0.4w%Aerosil 300 5 min. at 8000rpm d 1.5 g of 10w% of Sodium water 0.4 gprecursor dispersion in 0.1M HCl (IKA ultraturrax silicate(aq.)solution. S25N-10G) Conditions e H Oil in 1.6 g fragrance oil and J 8 gof a 0.4w% Aerosil 300 5 min. at 8000rpm d 1.5 g of TEOS. water 0.4 gprecursor dispersion in 0.1M HCl (IKA ultraturrax Conditions e S25N-10G)L Oil in 1.6 g MML(a) and 0.4 g J 8 g of a 0.4w% Aerosil 300 5 min. at8000rpm d 0.9 g of 5.4w% of Sodium water precursor dispersion in 0.1MHCl (IKA ultraturrax silicate(aq.) solution. S25N-10G) Conditions e QOil in 2 g fragrance oil and M 8 g of a 1.75w% Aerosil 300 5 min. at8000rpm d 0.9 g of 5.4w% of Sodium water 0.5 g precursor dispersion in0.1M HCl (IKA ultraturrax silicate(aq.) solution. S25N-10G) Conditions eS Oil in 20 g fragrance oil and J 80 g of a 2.5w% Aerosil 300 5 min. at1400rpm c 0.9 g of 5.4w% of Sodium water 5 g precursor dispersion in0.1M HCl (IKA R1342 silicate(aq.) solution. Propeller 4 bladed)Conditions e T Oil in 4 g fragrance oil and 1 g J 16 g of a 2.5w%Aerosil 300 5 min. at 8000rpm c 0.9 g of 5.4w% of Sodium water precursordispersion in 0.1M HCl (IKA ultraturrax silicate(aq.) solution.S25N-10G) Conditions e Z Oil in 1.2 g fragrance oil and M 8 g of a1.75w% Aerosil 300 5 min. at 8000rpm c 0.9 g of 5.4w% of Sodium water0.8 g precursor dispersion in 0.1M HCl (IKA ultraturrax silicate(aq.)solution. S25N-10G) Conditions e C Oil in 1.6 g MML(a) and 0.4 g J 8 gof a 0.4w% Aerosil 300 5 min. at 8000rpm d No second shell waterprecursor dispersion in 0.1M HCl (IKA ultraturrax component S25N-10G) EOil in 1.2 g fragrance oil and J 8 g of a 1.75w% Aerosil 300 5 min. at8000rpm d No second shell water 0.8 g precursor dispersion in 0.1M HCl(IKA ultraturrax component S25N-10G) I Oil in 2 g isopropyl myristate J8 g of a 1.75w% Aerosil 300 5 min. at 8000rpm d No second shell waterand 0.5 g precursor dispersion in 0.1M HCl (IKA ultraturrax componentS25N-10G) J Oil in 1.2 g Fragrance oil, J 8 g of a 1.75w% Aerosil 300 5min. at 8000rpm d No second shell water 0.8 g Isopropyl dispersion in0.1M HCl (IKA ultraturrax component myristate and 0.5 g S25N-10G)precursor K Oil in 4 g fragrance oil and 1 g AW 16 g of a 1.25w% Al₂O₃ 1min. at 13500rpm c No second shell water precursor nanopowder dispersionin DI (IKA ultraturrax component S25N-10G) N Water in 0.1 g ofprecursor, K 0.4 g of a 1w% Allura red 5 min. at 2500rpm d No secondshell oil 0.05 g of Aerosil R816 aqueous solution (vortex mixer).component and 4.85 g of hexyl salicylate AA Oil in 20 g fragrance oiland AZ 80 g of a 2.5w% Aerosil 300 1 min. at 6000rpm b Step 1) 1 gSnCl2, water 5 g of precursor dispersion in 0.1M HCl (IKA ultraturrax0.5 g HCL S25N-25) cc, 98.5 g DI water Step 2) 0.05 g PdCl2, 0.5 g HClcc., 100 g DI water Step 3) 3 g NiSO4(H₂O)6, 10 g NaPO2H2 and 87 g DIwater. Conditions h AB Oil in 4 g fragrance oil and 1 g AP 16 g of a1.25w% Aerosil 5 min. at 8000rpm c No second shell component waterprecursor 300 dispersion in 0.1M HCl (IKA ultraturrax S25N-10G) AC Oilin 4 g fragrance oil and 1 g AY 16 g of a 1.25w% Aerosil 5 min. at8000rpm c 1 mL of 1M CaCl₂ aqueous water precursor 300 dispersion in0.1M HCl (IKA ultraturrax solution and 1 mL of 1 M S25N-10G) Na₂CO₃aqueous solution. Conditions g AD Water in 0.1 g of precursor, K 0.4 gof a 1w% Allura red 5 min. at 2500rpm d 1 g of TEOS. Conditions e oil0.05 g of Aerosil R816 aqueous solution (vortex mixer). and 4.85 g ofhexyl salicylate Section A-Comparative example W Oil in 2 g fragranceoil and TEOS 8 g of a 1.75w% Aerosil 300 1 min. at 8000rpm d 1 g of 10w%of Sodium water 0.5 g precursor dispersion in 0.1M HCl (IKA ultraturraxsilicate(aq.) solution. S25N-10G) Conditions e Section B AF Oil in 4 gfragrance oil and 1 g O 16 g of a 1.25w% Aerosil 1 min. at 13400rpm b 1g of 10w% of Sodium water precursor 300 dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-10G) Conditions f AH Oil in 4 gfragrance oil and 1 g P 16 g of a 1.25w% Aerosil 1 min. at 13400rpm b 1g of 10w% of Sodium water precursor 300 dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-10G) Conditions f AJ Oil in 4 gfragrance oil and 1 g R 16 g of a 1.25w% Aerosil 1 min. at 13400rpm b 1g of 10w% of Sodium water precursor 300 dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-10G) Conditions f SectionB-Comparative Examples AE Oil in 4 g fragrance oil and l g O 16 g of a1.25w% Aerosil 1 min. at 13400rpm b No second shell component waterprecursor 300 dispersion in 0.1M HCl (IKA ultraturrax S25N-10G) AG Oilin 4 g fragrance oil and 1 g P 16 g of a 1.25w% Aerosil 1 min. at13400rpm b No second shell component water precursor 300 dispersion in0.1M HCl (IKA ultraturrax S25N-10G) AI Oil in 4 g fragrance oil and l gR 16 g of a 1.25w% Aerosil 1 min. at 13400rpm b No second shellcomponent water precursor 300 dispersion in 0.1M HCl (IKA ultraturraxS25N-10G) AK Oil in 4 g fragrance oil and 1 g P 16 g of a 1.25w% Aerosil1 min. at 13400rpm No second shell component water precursor and 0.26 g300 dispersion in 0.1M HCl (IKA ultraturrax MethylTriEthoxySilaneS25N-10G) AL Oil in 4 g fragrance oil and l g P 16 g of a 1.25w% Aerosil1 min. at 13400rpm b 1 g of 10w% of Sodium water precursor and 0.26 g300 dispersion in 0.1M HCl (IKA ultraturrax silicate(aq.) solution.MethylTriEthoxySilane S25N-10G) Conditions f AM Oil in 4 g fragrance oiland 1 g P 16 g of a 1.25w% Aerosil 1 min. at 13400rpm b No second shellcomponent water precursor and 0.65 g 300 dispersion in 0.1M HCl (IKAultraturrax MethylTriEthoxySilane S25N-10G) AN Oil in 4 g fragrance oiland l g 16 g of a 1.25w% Aerosil 1 min. at 13400rpm b 1 g of 10w%ofSodium water precursor and 0.65 g P 300 dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. MethylTriEthoxySilane S25N-10G)Conditions f AO Oil in 4 g fragrance oil and 1 g P 16 g of a 1.25w%Aerosil 1 min. at 13400rpm b No second shell component water precursorand 1.3 g 300 dispersion in 0.1M HCl (IKA ultraturraxMethylTriEthoxySilane S25N-10G) AP Oil in 4 g fragrance oil and 1 g P 16g of a 1.25w% Aerosil 1 min. at 13400rpm b 1 g of 10w% of Sodium waterprecursor and 1.3 g 300 dispersion in 0.1M HCl (IKA ultraturraxsilicate(aq.) solution. MethylTriEthoxySilane S25N-10G) Conditions fSection C AU Oil in 2 g fragrance oil and AAA 16 g of a 3w% Aerosil 3001 min. at 21400rpm b No second shell component water 1.2 g precursordispersion in 0.1M HCl (IKA ultraturrax S25N-10G) AV Oil in 4 gfragrance oil and 1 g AW 16 g of a 1.25w% Aerosil 1 min. at 24000rpm c 2g of 10w% of Sodium water of precursor 300 dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-10G) Conditions f SectionC-Comparative Examples B Oil in 2 g fragrance oil and J 8 g of a 1.75w%Aerosil 300 5 min. at 8000rpm d No second shell component water 0.5 gprecursor dispersion in 0.1M HCl (IKA ultraturrax S25N-10G) AQ Oil in1.6 g fragrance oil and AW 8 g of a 3w% Aerosil 300 1 min. at 24000rpm cNo second shell component water 0.4 g precursor dispersion in 0.1M HCl(IKA ultraturrax S25N-10G) AR Oil in 1.75 g fragrance oil and AW 8 g ofa 3w% Aerosil 300 1 min. at 24000rpm c No second shell component water0.75 g precursor dispersion in 0.1M HCl (IKA ultraturrax S25N-10G) ASOil in 3 g fragrance oil and AAA 16 g of a 3w% Aerosil 300 1 min. at17400rpm b No second shell component water 1.2 g precursor dispersion in0.1M HCl (IKA ultraturrax S25N-10G) AT Oil in 4 g fragrance oil and 1 gAAD 16 g of a 1.25w% Aerosil 1 min. at 24000rpm c 2 g of 10w% of Sodiumwater of precursor 300 dispersion in 0.1M HCl (IKA ultraturraxsilicate(aq.) solution. S25N-10G) Conditions f AW Oil in 4.75 gfragrance oil and AX 16 g of a 0.20w% Aerosil 1 min. at 3000rpm b Nosecond shell component water 0.25 g of precursor 300 dispersion in 0.1MHCl (IKA ultraturrax S25N-10G) Section D AAA Oil in 4 g fragrance oiland 1 g AY 16 g of a 1.25w% Aerosil 5 min. at 800rpm c 2 g of 10w% ofSodium water of precursor 300 dispersion in 0.1M HCl (IKA ultraturraxsilicate(aq.) solution. S25N-10G) Conditions f AAB Oil in 4 g fragranceoil and 1 g AAC 16 g of a 2.5w% Aerosil 300 1 min. at 13500rpm b 2 g of10w% of Sodium water of precursor dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-10G) Conditions f AAC Oil in 20g fragrance oil and AZ 80 g of a 2.5w% Aerosil 300 1 min. at 6000rpm b 2g of 10w% of Sodium water 5 g of precursor dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-25) Conditions f SectionD-Comparative Examples AAD Oil in 1.6 g fragrance oil and TEOS 8 g of a0.5w% Aerosil 300 1 min. at 8000rpm b 1 g of 10w% of Sodium water 0.4 gof precursor dispersion in 0.1M HCl (IKA ultraturrax silicate(aq.)solution. S25N-10G) Conditions f AAE Oil in 1.6 g fragrance oil andDynasylan 8 g of a 0.5w% Aerosil 300 1 min. at 8000rpm b 1 g of 10w% ofSodium water 0.4 g of precursor 40 dispersion in 0.1M HCl (IKAultraturrax silicate(aq.) solution. S25N-10G) Conditions f AAF Oil in1.6 g fragrance oil and TBOS 8 g of a 0.5w% Aerosil 300 1 min. at8000rpm d 1 g of 10w% of Sodium water 0.4 g of precursor dispersion in0.1M HCl (IKA ultraturrax silicate(aq.) solution. S25N-10G) Conditions fAX Oil in 4 g fragrance oil and 1 g AAB 16 g of a 1.25w% Aerosil 5 min.at 8000rpm c 2 g of 10w% of Sodium water of precursor 300 dispersion in0.1M HCl (IKA ultraturrax silicate(aq.) solution. S25N-10G) Conditions fAY Oil in 4 g fragrance oil and l g G 16 g of a 1.25w% Aerosil 5 min. at8000rpm 2 g of 10w% of Sodium water of precursor 300 dispersion in 0.1MHCl (IKA ultraturrax silicate(aq.) solution. S25N-10G) Conditions f

Conditions Referenced in Table 3

a. Menthol menthyl lactate (MML) was prepared by mixing Menthol andMenthyl Lactate at a weight ratio of 1:1 which yields a liquid at roomtemperature (U.S. Pat. No. 6,897,195B2 discloses how such mixture can bemade, the disclosure of which is incorporated herein by reference).

b. Curing 4 h at RT, 16 h at 50° C. and 96 h at 70° C.

c. Curing at 50° C. for 3 weeks

d. Curing at RT for over 5 weeks

e. The slurry was diluted 20× in 0.1HCl and treated with the secondshell component precursor solution, which was added dropwise using aplastic pipette under constant agitation of 350 RPM using an overheadstirrer, at room temperature and pH 1.2. The capsules were kept underagitation at 300 RPM for 24 hours, then centrifuged for 10 minutes at2500 rpm and re-dispersed in DI water/

f. The slurry was diluted 4×in 0.1HCl and treated with a controlledaddition (10 μl per minute) of the second shell component precursorsolution, using a suspended magnetic stirrer reactor at 350 RPM, at roomtemperature. The pH was kept constant at pH 7 using 1M HCl(aq) and 1MNaOH (aq) solutions. The capsules were kept under agitation at 300 RPMper 24 hours, then centrifuged per 10 minutes at 2500 rpm andre-dispersed in DI water.

g. The slurry is diluted 10× in Di water and treated with controlledaddition of aqueous CaCl₂ (1 M, 1 ml) and Na₂CO₃ (1 M, 1 ml) over 1 hourusing a suspended magnetic stirrer reactor at 350 RPM. The pH was keptconstant at pH 7 using 1M HCl(aq) and 1M NaOH (aq) solutions. Thecapsules are kept under agitation at 300 RPM per 24 hours, thencentrifuged per 10 minutes at 2500 rpm and re-dispersed in DI water.

h. Before each step and after step (3), the slurry must be washed with10 g DI water, centrifuged for 10 minutes at 1500 rpm and separating thesupernatant, 3 times. Step (1) and (2) slurry is added to solution, andthe mixture is shaken with lab shaker for 10 minutes at RT. Step (3)slurry is added to solution and is shaken with overhead mixer at 150 rpmfor 1 h at 60 C.

TABLE 4 Examples results Section A Mean Thickness to Effective NominalMean Shell Diameter core to wall Shell Diameter CoV PSD Thickness ratioshell Shell tension Permeability Survive Sample ID (nm) (%) (um) (%)ratio % organic (N/m) (%) drying F 24.8 33.5 0% 12.3 Yes G 31.8 30.5768.8 2.4% 85:15 0% 2.4 Yes H 31.8 30.5 868.3 2.7% 84:16 0% 2.6 Yes L62.3 18.2 0% Yes Q 15.8 37.2 0% Yes S 90.5 38.6 437.0 0.5% 97:3  0% 3.834.1%  Yes T 24.4 27.2 675.5 2.8% 84:16 0% 2.1 11.9%  Yes Z 16.4 38.3526.1 3.20%  82:18 0% Yes C 31.8 30.5 768.8 2.4% 86:14 0% 1.6 Yes E 17.439.4 562.0 3.2% 82:18 0% 4.6 Yes I 20.0 31.8 427.3 2.1% 88:12 0% 5.3 YesJ 17.1 31.9 475.1 2.8% 84:16 0% 1.6 Yes K 0% Yes AA 29.50 25.6 0% Yes AB55.75 31.6 0% Yes AC 33.25 30.3 0% Yes Section A-Comparative Example W21.3 39.1 Footnote “a” 0% No Section B AF 22.1 30.6 1.8%   36% Yes AH25.5 33.8 4.2%   17% Yes AJ 25.6 33.9 3.4%   27% Yes SectionB-Comparative Examples AE 22.1 30.6 1.8%   91% Yes AG 25.5 33.8 4.2%  96% Yes Al 25.6 33.9 3.4%   74% Yes AK 32.2 40.5 6.8%   98% Yes AL 32.240.5 6.8%   52% Yes AM 32.4 35.1 9% 71% Yes AN 32.4 35.1 9% NA^(b) YesAO 34.3 37.6 12%  70% Yes AP 34.3 37.6 12%  NA^(b) Yes Section C AU 14.436 408 2.8% 84:16 0% 23% Yes AV 41.4 34 311 0.8% 95:5  0% 29% YesSection C-Comparative Examples B 16.2 32.0 646.0 4.0% 78:22 0% 1.2 83%Yes AQ 5.28 36.63 103.5 2.0% 90:10 0% 100%  Yes AR 10.5 55 164.1 1.6%87:13 0% 100%  Yes AS 13.06 51 515.7 4.0% 77:23 0% 74% Yes AT 31 31.264.2 0.2% 99:1  0% 65% Yes AW 144.9 15.14 287.5 0.2% 99:1  0% 100%  YesSection D AAA 37.5 24.7 371.2 1.0% 92:8  0% 20% yes AAB 25.4 53.7 160.50.6% 94:6  0% 13% yes AAC 26.6 33.5 0% 25% yes Section D-ComparativeExamples AX 37 32.5 395.2 1.1% 92:8  0% 79% yes AY 40.3 52.36 Footnote“a” 0% 89% No AAD 43.6 56.4 Footnote “a” 0% 81% No AAE 34.6 58.3Footnote “a” 0% 79% No AAF 14.5 41.5 Footnote “a” 0% 100%  No^(a)Comparative examples: capsules collapsed when dried on microslide,the measurement was not possible. ^(b)Second shell component was notplaced as slurry was too viscous.

For all examples below, the following method was used to test ifcapsules collapse: 0.1 gr of slurry was diluted into 5 gr of DI water.Of this dilution, a few drops were added onto a microslide, and thecapsules were let air drying until all water had evaporated. Whenobserving the dry slurry with an optical microscope, one could thendetermine if capsules were not collapsing if they maintain their initialspherical shape.

The below Examples 8-1, and Comparative Examples 8-2 and 8-3 show theimportance of using precursors as disclosed in this invention incombination with nanoparticles and a second shell component as disclosedin this invention, in order to obtain low shell permeabilities.

Example 8-1

The water phase was prepared by weighing 1.25 gr of Aerosil 300 andbringing the total weight to 100 gr with 0.1M HCl. The nanoparticleswere dispersed by sonicating the mixture in an ultrasonic bath for atleast 30 minutes or until no more solid sediments.

The oil phase was prepared by mixing and homogenizing 1 gr of precursorAY with 4 gr of a fragrance mixture of formula A (see below).

16 gr of the water phase was mixed with the above oil phase with anultraturrax (S25N-Og mixing tool from IKA) at 13500 rpm for 1 minute.The resulting mixture was capped with an airtight lid, let standing for4 hours at room temperature, and an additional 3 weeks at 50 C. After 3weeks at 50 C, the capsules slurry was formed. The capsules were notcollapsing on a microslide.

The slurry was diluted 4× in 0.1HCl and treated with a controlledaddition (10 μl per minute) of 2 gr of a 10 w % solution of SodiumSilicate (aq.), using a suspended magnetic stirrer reactor at 350 RPM,at room temperature. The pH was kept constant at pH 7 using 1M HCl(aq)and 1M NaOH (aq) solutions. The capsules were kept under agitation at300 RPM per 24 hours, then centrifuged per 10 minutes at 2500 rpm andre-dispersed in DI water.

The resulting capsule slurry was put through the permeability test asdisclosed in this invention, and the shell permeability % was 21% basedon the permeability test.

Comparative Example 8-2

The water phase was prepared by diluting a 25 w % CTAC (aq.) solution(supplied by Sigma Aldrich) into DI water, to reach a concentration of0.52 w % of CTAC.

The oil phase was made by mixing 40 gr of Fragrance of formula (A) and10 gr of TEOS. The above oil phase was mixed with 100 gr of the abovewater phase using an ultraturrax mixer (S25N mixing tool from IKA), at8500 rpm for 1 minute. The resulting emulsions pH was trimmed to 3.9with the use of 1M NaOH (supplied by sigma Aldrich). Then, the emulsionwas continuously stirred at 160 rpm with an overhead mixer and heated at30 C for 17 hours in a jacketed reactor that was covered to avoidevaporation of water or any other components. After the 17-hour reactiontime, capsules had formed. The capsules were collapsing when air dried.

The resulting capsule slurry was put through the permeability test asdisclosed in this invention, and the shell permeability % was 67% basedon the permeability test.

Comparative Example 8-3

Same as comparative example 8-1, except that after the capsule slurrywas formed, the pH was trimmed to 3.2 and 5.7 g of TEOS was addeddropwise over 320 minutes while the temperature was maintained at 30 Cand mixing speed at 160 rpm with an overhead mixer. After all the TEOSwas added, the slurry was mixed for an additional 18 hours at 30 C and160 rpm with an overhead mixer, to obtain capsules. The capsules werenot collapsing when air dried.

The resulting capsule slurry was put through the permeability test asdisclosed in this invention, and the shell permeability % was 67% basedon the permeability test.

Fragrance Formula (A):

Hexyl acetate 9 w %Methyl dihydrojasmonate 9 w %

Tetrahydrolinalol 9 w % α-Ionone 9 w % Lilial 18 w %

Hexylcinnamyl aldehyde 18 w %Hexyl salicylate 18 w %

Verdyl Acetate 10 w %

The below Examples 9-1 and comparative examples 9-2 and 9-3 show theimportance of using precursors as disclosed in this invention incombination with nanoparticles and a second shell component as disclosedin this invention, in order to obtain low shell permeabilities.

Example 9-1

Example ID AAA from Table 3. Capsules were not collapsing when left airdrying and had a permeability % of 20% in the permeability test.

Comparative Example 9-2

In a 50 m round bottomed flask equipped with a magnetic stir bar, 4 grof 0.01M HCl (a.q.) was combined with 3 gr Phenyltriethoxysilane(PhTEOS). Initially the two phases were not miscible. Next, the mixturewas vigorously stirred at 1000 rpm while trimming the pH to 2 with 0.1MNaOH. The mixture was stirred at 1000 rpm and Room temperature untilobtaining a homogeneous mixture. This yielded a precursor mixture.

Next, 1.5 gr of the same fragrance as for example AAA was added to 48.5gr of water containing 18 mg of a 50 w % CTAC solution. The resultingmixture was stirred with a magnetic stirbar for 30 minutes at roomtemperature, after which 2.5 ml of 25 w % ammonia was added and 5 ml ofthe above prepared precursor mixture. This was stirred for an additional2 hours, after which capsules were formed. The capsules were collapsingafter left air drying. The capsules had a permeability % of 99% based onthe permeability test.

Comparative Example 9-3

144 gr of the same fragrance as for example AAA was weighed in a vessel.In a separate vessel, 96 gr of a 1 w % CTAC solution was created bymixing 3.84 gr of a 25 w % CTAC solution and bringing the mass to 96 grwith DI water. The above fragrance was mixed with the above surfactantmixture with an IKA ultraturrax mixer (S25N mixing tool) at 8000 rpm for5 minutes.

Next, 144 gr of water with a pH of 3.8 (trimmed with Concentrated HCl)was added to the above prepared emulsion system.

Next, 27 gr of a mixture containing 26.73 gr of TEOS and 0.27 gr ofDimethylDiethoxysilane was added dropwise to the emulsion system underconstant mixing. When all of the precursor was added, the mixture washeated to 50 C and stirred at 200 rpm with an overhead mixer in ajacketed reactor for 2 hours.

The resulting capsules were collapsing when left air drying, and thecapsules had a permeability % of 77% as determined by the permeabilitytest.

The below Examples 10-1, and 10-3 and Comparative Examples 10-2, 10-4,10-5 and 10-6 show the importance in choosing the right precursors,nanoparticles and second shell components as disclosed in this inventionto obtain capsules with low permeabilities.

Example 10-1

The water phase was prepared by weighing 1.25 gr of Aerosil 300 andbringing the total weight to 100 gr with 0.1M HCl. The nanoparticleswere dispersed by sonicating the mixture in an ultrasonic bath for atleast 30 minutes or until no more solid sediments.

The oil phase was prepared by mixing and homogenizing 1 gr of precursorAY with 3.5 gr of Isopropyl Myristate and 0.5 gr of Verdyl acetate. 16gr of the above water phase was mixed with the above oil phase with anultraturrax (S25N-10 g mixing tool from IKA) at 13500 rpm for 1 minute.The resulting mixture was capped with an airtight lid, let standing for4 hours at room temperature, and an additional 3 weeks at 50 C.

After 3 weeks at 50 C, the capsules slurry was formed. The capsules werenot collapsing on a microslide. No second shell component was added forthis capsule, and the capsules permeability % was 40% based on thepermeability test.

Comparative Example 10-2

Same process as for example ID AAC from Table 3, except that no secondshell component was added. The capsules survived drying and the capsulepermeability % was 98% based on the permeability test.

Example 10-3

Example ID AAC from Table 3. The capsules survived drying and thecapsule permeability % was 25% based on the permeability test.

Comparative Example 10-4

The oil phase was prepared by mixing 20 gr of TEOS, 115 gr of IsopropylMyristate and 15 gr of Verdyl acetate.

Next, the water phase was prepared by weighing 10 gr of a 25 w % CTAC(aq.) solution and bringing the weight to 150 gr with DI water to reacha CTAC concentration of 1.67 w %.

The two phases were mixed together with a Ultraturrax mixer (S25N toolfrom IKA) at 6000 rpm for 1 minute. Next, 50 g of Ludox TM50 was addedand the system was further mixed at 8000 rpm for another 1 minute. Next,the pH was adjusted to 5 with 1M HCl.

To the above mixture, 50 gr of 10 w % PVOH in water (selvol 540) and 5gr of a 25 w % sodium silicate in water were added. The pH was thenreadjusted to 4, and the system stirred at Room temperature at 200 rpmwith an overhead mixer for 20 hours. The capsules were collapsing whenleft air drying on a microslide and the capsules permeability % was 92%based on the permeability test.

Comparative Example 10-5

Same as Comparative Example 10-4, except 40 gr of a 5 w % polyquaternium7 aqueous solution was further added at the end after formation ofcapsules. The capsules were collapsing when left air drying on amicroslide and the capsule permeability % was 83% based on thepermeability test.

Comparative Example 10-6

Same process as for comparative example 10-2 above, except that 1.3 grof a 5 w % solution of polyquaternium 7 aqueous solution was furtheradded to 5 gr of slurry, and the mixture was stirred at 200 rpm with anoverhead mixer for 15 minutes. The capsules survived drying and thecapsule permeability % was 73% based on the permeability test.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A population of capsules, the capsulescomprising: An oil-based core comprising a benefit agent, and asubstantially inorganic shell surrounding the core, wherein the shellcomprises a first shell component comprising at least one of a metaloxide or a semi-metal oxide, wherein the first shell component comprisesup to 5 wt % of organic content; wherein said population has a meanvolume weighted capsule diameter of about 10 micrometers to about 200micrometers, an average shell thickness of about 170 nm to about 1000nm; and wherein the mean volumetric core-shell ratio is from about 80:20to about 98:2.
 2. The population of capsules according to claim 1,wherein said population has a shell permeability from about 0.01% toabout 40%.
 3. The population of capsules according to claim 1, whereinsaid population has a shell permeability from about 0.01% to about 30%.4. The population of capsules according to claim 1, wherein saidpopulation has a shell permeability from about 0.01% to about 20%. 5.The population of capsules according to claim 1, wherein the benefitagent comprises at least one of chromogens and dyes, perfumecompositions, perfume raw materials, lubricants, silicone oils, waxes,hydrocarbons, higher fatty acids, essential oils, lipids, skin coolants,vitamins, sunscreens, antioxidants, catalysts, malodor reducing agents,odor-controlling materials, softening agents, insect and moth repellingagents, colorants, pigments, pharmaceuticals, pharmaceutical oils,adhesives, bodying agents, drape and form control agents, smoothnessagents, wrinkle control agents, sanitization agents, disinfectingagents, germ control agents, mold control agents, mildew control agents,antiviral agents, drying agents, stain resistance agents, soil releaseagents, fabric refreshing agents and freshness extending agents,chlorine bleach odor control agents, dye fixatives, color maintenanceagents, color restoration/rejuvenation agents, anti-fading agents,anti-abrasion agents, wear resistance agents, fabric integrity agents,anti-wear agents, anti-pilling agents, defoamers, anti-foaming agents,UV protection agents, sun fade inhibitors, anti-allergenic agents,fabric comfort agents, shrinkage resistance agents, stretch resistanceagents, stretch recovery agents, skin care agents and natural actives,dyes, phase change materials, fertilizers, nutrients, or herbicides. 6.The population of capsules according to claim 5, wherein the benefitagent comprises perfume compositions.
 7. The population of capsulesaccording to claim 5, wherein the oil-based core comprising a benefitagent, further comprises a core modifier.
 8. The population of capsulesaccording to claim 1, wherein the first shell component comprises up to2 wt % of organic content.
 9. The population of capsules according toclaim 1, wherein the first shell component comprises inorganicnanoparticles that are at least one of metal nanoparticles, mineralnanoparticles, metal-oxide nanoparticles or semi-metal oxidenanoparticles.
 10. The population of capsules according to claim 9,where the inorganic nanoparticles comprise at least one of SiO₂, TiO₂,Al₂O₃, Fe₂O₃, Fe₃O₄, CaCo₃, clay, silver, gold, and copper.
 11. Thepopulation of capsules according to claim 1, wherein the shell furthercomprises an inorganic second shell component surrounding the firstshell component, wherein the inorganic second shell component comprisesan inorganic second shell material that is at least one of SiO₂, TiO₂,Al₂O₃, CaCO₃, Ca₂SiO₄, Fe₂O₃, Fe₃O₄, iron, silver, nickel, gold, copper,and clay.
 12. The population of capsules according to claim 11, whereinthe second shell component comprises at least one of SiO₂ or CaCO₃. 13.The population of capsules according to claim 1, wherein the first shellcomponent comprises a condensed layer comprising a condensation productof a precursor of formula (I):(M^(v)O_(z)Y_(n))_(w)  (Formula I), where M is one or more of silicon,titanium and aluminum, v is the valence number of M and is 3 or 4, z isfrom 0.5 to 1.6, each Y is independently selected from —OH, —OR², halo,

—NH₂, —NHR², —N(R²)₂, and

wherein R² is a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ to C₂₂ aryl, ora 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatomsselected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ to C₂₀alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprising from1 to 3 ring heteroatoms selected from O, N, and S, n is from 0.7 to(v-1), and w is from 2 to
 2000. 14. The population of capsules accordingto claim 13, wherein for formula (I): M is Si, Y is OR₂, and R₂ is alinear or branched alkyl chain comprising 1 to 4 carbon atoms.
 15. Thepopulation of capsules according to claim 13, wherein for formula (I): Mis Si, Y is OR₂ and R₂ is an ethyl group.
 16. The population of capsulesaccording to claim 13, wherein precursors of formula (I) have amolecular weight between 700 Da and 30,000 Da.
 17. The population ofcapsules according to claim 16, wherein precursors of formula (I) have adegree of branching between 0.2 and 0.6.
 18. The population of capsulesaccording to claim 13, wherein precursors of formula (I) have a PDIbetween 1 and
 20. 19. The population of capsules according to claim 13,wherein precursors of Formula (I) can be combined with TEOS, TMOS andTBOS.
 20. The population of capsules according to claim 1, wherein thefirst shell component comprises a condensed layer comprising acondensation product of a precursor of formula (II):(M^(v)O_(z)Y_(n)R¹ _(p))_(w)  (Formula II), where M is one or more ofsilicon, titanium and aluminum, v is the valence number of M and is 3 or4, z is from 0.5 to 1.6, each Y is independently selected from —OH,—OR², halo,

NH₂, —NHR², —N(R²)₂,

wherein R² is selected from a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ toC₂₂ aryl, or a 5-12 membered heteroaryl comprising from 1 to 3 ringheteroatoms selected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ toC₂₀ alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprisingfrom 1 to 3 ring heteroatoms selected from O, N, and S, n is from 0 to(v-1), each R¹ is independently selected from a C₁ to C₃₀ alkyl, a C₁ toC₃₀ alkylene, a C₁ to C₃₀ alkyl substituted with one or more of ahalogen, —OCF₃, —NO₂, —CN, —NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino,mercapto, acryloyl, CO₂H, CO₂alkyl, aryl, and heteroaryl, or a C₁ to C₃₀alkylene substituted with one or more of a halogen, —OCF₃, —NO₂, —CN,—NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO₂H,CO₂alkyl, aryl, and heteroaryl, p is present in an amount up to pmax,and w is from 2 to 2000; wherein pmax=60/[9*Mw(R¹)+8], where Mw(R¹) isthe molecular weight of the R¹ group.
 21. The population of capsulesaccording to claim 20, wherein for formula (II): M is Si, Y is OR₂, andR₂ is a linear or branched alkyl chain comprising 1 to 4 carbon atoms.22. The population of capsules according to claim 20, wherein forformula (II): M is Si, Y is OR₂ and R₂ is an ethyl group.
 23. Thepopulation of capsules according to claim 20, wherein precursors offormula (II) have a molecular weight between 700 Da and 30,000 Da. 24.The population of capsules according to claim 23, wherein precursors offormula (II) have a degree of branching between 0.2 and 0.6.
 25. Thepopulation of capsules according to claim 20, wherein precursors offormula (II) have a PDI between 1 and
 20. 26. The population of capsulesaccording to claim 1, wherein the capsules have a mean nominal walltension of about 0.1 N/m to about 50 N/m.
 27. The population of capsulesaccording to claim 26, wherein the capsules have a mean nominal walltension of about 0.5 N/i to about 30 N/m.
 28. A population of capsules,the capsules comprising: a water-based core comprising a benefit agent,and a substantially inorganic shell surrounding the core, wherein theshell comprises a first shell component comprising at least one of ametal oxide or a semi-metal oxide, wherein the first shell componentcomprises up to about 5 wt % of organic content; wherein said populationhas a mean volume weighted capsule diameter of about 10 micrometers toabout 200 micrometers, an average shell thickness of about 170 nm toabout 1000 nm; and wherein the mean volumetric core-shell ratio is fromabout 80:20 to about 98:2.
 29. The population of capsules according toclaim 28, wherein the benefit agent comprises at least one of perfumeraw materials, perfume compositions, skin coolants, vitamins,sunscreens, antioxidants, glycerin, bleach encapsulates, chelatingagents, antistatic agents, insect and moth repelling agents, colorants,antioxidants, sanitization agents, disinfecting agents, germ controlagents, mold control agents, mildew control agents, antiviral agents,drying agents, stain resistance agents, soil release agents, chlorinebleach odor control agents, dye fixatives, dye transfer inhibitors,color maintenance agents, optical brighteners, colorrestoration/rejuvenation agents, anti-fading agents, whitenessenhancers, anti-abrasion agents, wear resistance agents, fabricintegrity agents, anti-wear agents, anti-pilling agents, defoamers,anti-foaming agents, UV protection agents, sun fade inhibitors,anti-allergenic agents, enzymes, water proofing agents, fabric comfortagents, shrinkage resistance agents, stretch resistance agents, stretchrecovery agents, skin care agents, and natural actives, antibacterialactives, antiperspirant actives, cationic polymers, dyes, metalcatalysts, non-metal catalysts, activators, pre-formed peroxy carboxylicacids, diacyl peroxides, hydrogen peroxide sources, or enzymes.
 30. Thepopulation of capsules according to claim 9, wherein the water-basedcore comprising a benefit agent further comprises a core modifier. 31.The population of capsules according to claim 28, wherein the firstshell component comprises up to 2 wt % of organic content.
 32. Thepopulation of capsules according to claim 28, wherein the first shellcomponent comprises inorganic nanoparticles that are at least one ofmetal nanoparticles, mineral nanoparticles, metal-oxide nanoparticles orsemi-metal oxide nanoparticles.
 33. The population of capsules accordingto claim 32, where the inorganic nanoparticles comprise at least one ofSiO₂, TiO₂, Al₂O₃, Fe₂O₃, Fe₃O₄, CaCo₃, clay, silver, gold, and copper.34. The population of capsules according to claim 28, wherein the shellfurther comprises an inorganic second shell component surrounding thefirst shell component, wherein the inorganic second shell componentcomprises an inorganic shell material that is at least one of SiO₂,TiO₂, Al₂O₃, CaCO₃, Ca₂SiO₄, Fe₂O₃, Fe₃O₄, iron, silver, nickel, gold,copper, and clay.
 35. The population of capsules according to claim 34,wherein the second shell component comprises at least one of SiO₂ orCaCO₃.
 36. The population of capsules according to claim 28, wherein thefirst shell component comprises a condensed layer comprising acondensation product of a precursor of formula (I):(M^(v)O_(z)Y_(n))_(w)  (Formula I), where M is one or more of silicon,titanium and aluminum, v is the valence number of M and is 3 or 4, z isfrom 0.5 to 1.6, each Y is independently selected from —OH, —OR², halo,

—NH₂, —NHR², —N(R²)₂, and

wherein R² is a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ to C₂₂ aryl, ora 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatomsselected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ to C₂₀alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprising from1 to 3 ring heteroatoms selected from O, N, and S, n is from 0.7 to(v-1), and w is from 2 to
 2000. 37. The population of capsules accordingto claim 36, wherein for formula (I): M is Si, Y is OR₂, and R₂ is alinear or branched alkyl chain comprising 1 to 4 carbon atoms.
 38. Thepopulation of capsules according to claim 36, wherein for formula (I): Mis Si, Y is OR₂ and R₂ is an ethyl group.
 39. The population of capsulesaccording to claim 36, wherein precursors of formula (I) have amolecular weight between 700 Da and 30,000 Da.
 40. The population ofcapsules according to claim 39, wherein precursors of formula (I) have adegree of branching between 0.2 and 0.6.
 41. The population of capsulesaccording to claim 36, wherein precursors of formula (I) have a PDIbetween 1 and
 20. 42. The population of capsules according to claim 36,wherein precursors of Formula (I) can be combined with TEOS, TMOS andTBOS.
 43. The population of capsules according to claim 28, wherein thefirst shell component comprises a condensed layer comprising acondensation product of a precursor of formula (II):(M^(v)O_(z)Y_(n)R¹ _(p))_(w)  (Formula II), where M is one or more ofsilicon, titanium and aluminum, v is the valence number of M and is 3 or4, z is from 0.5 to 1.6, each Y is independently selected from —OH,—OR², halo,

—NH₂, —NHR², —N(R²)₂,

wherein R² is selected from a C₁ to C₂₀ alkyl, C₁ to C₂₀ alkylene, C₆ toC₂₂ aryl, or a 5-12 membered heteroaryl comprising from 1 to 3 ringheteroatoms selected from O, N, and S, R³ is a H, C₁ to C₂₀ alkyl, C₁ toC₂₀ alkylene, C₆ to C₂₂ aryl, or a 5-12 membered heteroaryl comprisingfrom 1 to 3 ring heteroatoms selected from O, N, and S, n is from 0 to(v-1), each R¹ is independently selected from a C₁ to C₃₀ alkyl, a C₁ toC₃₀ alkylene, a C₁ to C₃₀ alkyl substituted with one or more of ahalogen, —OCF₃, —NO₂, —CN, —NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino,mercapto, acryloyl, CO₂H, CO₂alkyl, aryl, and heteroaryl, or a C₁ to C₃₀alkylene substituted with one or more of a halogen, —OCF₃, —NO₂, —CN,—NC, —OH, —OCN, —NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO₂H,CO₂alkyl, aryl, and heteroaryl, p is present in an amount up to pmax,and w is from 2 to 2000; wherein pmax=60/[9*Mw(R¹)+8], where Mw(R¹) isthe molecular weight of the R¹ group.
 44. The population of capsulesaccording to claim 43, wherein for formula (II): M is Si, Y is OR₂, andR₂ is a linear or branched alkyl chain comprising 1 to 4 carbon atoms.45. The population of capsules according to claim 43, wherein forformula (II): M is Si, Y is OR₂ and R₂ is an ethyl group.
 46. Thepopulation of capsules according to claim 43, wherein precursors offormula (I) have a molecular weight between 700 Da and 30,000 Da. 47.The population of capsules according to claim 46, wherein precursors offormula (I) have a degree of branching between 0.2 and 0.6.
 48. Thepopulation of capsules according to claim 43, wherein precursors offormula (II) have a PDI between 1 and
 20. 49. The population of capsulesaccording to claim 28, wherein the capsules have a mean nominal walltension of about 0.1 N/m to about 50 N/m.
 50. The population of capsulesaccording to claim 49, wherein the capsules have a mean nominal walltension of about 0.5 N/m to about 30 N/m.